Water-soluble portion packaging with a filling

ABSTRACT

A portioned package of an active ingredient, including a sealed water-soluble envelope containing at least one core and a matrix of a free-flowing material at least partially surrounding the core, the core and matrix together including one or more active ingredients, wherein the core is fixed to the water-soluble envelope.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation under 35 U.S.C. § 365(c) and 35 U.S.C. § 120 of international application PCT/EP2003/012443, filed on Nov. 7, 2003. This application also claims priority under 35 U.S.C. § 119 of DE 102 53 213.3, filed Nov. 15, 2002, which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

The present invention is situated in the field of portioned compositions, which preferably possess detersive properties. Such detergent portions include, for example, portioned compositions for laundering textiles, portioned detergents for automatic dishwashers or for cleaning hard surfaces, portioned bleaching agents for use in washing machines or dishwashers, portioned water softeners or scouring salts; in the following, these individual types of products are summarized by the term “detergent portion”.

In particular, the invention relates to detergent portions, which are used for automatic dishwashing in domestic dishwashers.

Portioned detergents are widely described in the prior art and due to their ease of dosing find increasing popularity with consumers. Portioning can be achieved, for example, by conversion into a compact shape or by separate packaging. In the first case, tabletting plays a prominent roll, and in the latter case, portions are predominantly used in the field of detergents, which are enclosed in packaging made of water-soluble materials.

Detergent tablets possess a number of advantages over powder forms: They are simpler to dose and to handle, and due to their compact structure have advantages in storage and transport. Detergent molded bodies are also extensively described in the patent literature. One problem that arises repeatedly with the use of detergent molded bodies is the low rate of disintegration and dissolution of the molded body under the conditions of use. As adequately stable, i.e. dimensionally stable and fracture-resistant molded bodies can only be manufactured under relatively high molding pressures, there results a high compaction of the constituents of the molded body and a consequently delayed disintegration in the cleaning water and therefore a too slow a release of the active substances in the washing or cleaning process. The delayed disintegration of the molded body has also the disadvantage that many detergent molded bodies cannot be rinsed into domestic washing machines through the dispensing draw, because the tablets do not disintegrate rapidly enough into secondary particles that are small enough to be rinsed out of the dispensing draw into the cylinder of the washing machine.

This dichotomy between hardness (i.e. handleability) and disintegration plays only a minor role in packaged detergent portions. Here, phenomena such as solubility or disintegratability of the packaging come to the fore, while the packaged detergent and its physical properties only play a role when a tablet is packaged.

Admittedly, these portions have the disadvantage of not possessing the high degree of compactness as is found in tablets. Filling tubular pouches leads firstly to a low degree of compaction, secondly to a technically defined filling space, so that a measured amount of detergent required for a washing or cleaning process needs a larger volume than the corresponding amount in tablet form. In addition, the empty space means that filled pouches are not stable towards mechanical influences and can burst.

Moreover, filled pouches possess only limited aesthetic appeal. The consumer shows limited acceptance of this type of product offering and has little confidence in the performance of the product. If only one uniform composition is packaged in a pouch then in addition, the multifunctional advantages of the product cannot be visualized.

Furthermore, there is the problem that the lower density of the packaged composition in comparison to that of tablets, can lead to problems of space in the dishwasher's dispensing device. This means that to enable the portion to be added, less must be dosed, leading to worsened cleaning results.

Thus, packaging made of water-soluble materials are described in the prior art, which are not in the form of tubular pouches, but are rather manufactured by injection molding or deep drawing. These rigid objects are—similar to yoghurt pots—filled and sealed after filling. Indeed, should one fill larger solid objects in these packages, so as to suggest multi-usage, and surround them with a further composition (for example a powder, a liquid or a melt), then the solids can separate uncontrollably, thus leading to problems when sealing the filled hollow bodies and worsened aesthetic appeal.

The object of the present invention was to provide aesthetically appealing detergent portions, which combine the advantages of compactness of tablets with those of rapid dissolution of portioned systems. Here, larger solid bodies (“cores”), i.e. solids, which are markedly differentiated in size from particulate compositions and for example have a minimum diameter of greater than 2 mm, are included, without concomitant technical or aesthetic disadvantages.

It has now been found that cores can be inserted into water-soluble packaging portions and surrounded with free-flowing material if they are fixed to the water-soluble envelope prior to filling with free-flowing material.

The subject of the present invention in a first embodiment, is a portion packaging, comprising a water-soluble envelope together with at least one core therein and a matrix of a pourable material, at least partially surrounding the core(s), whereby the core(s) is/are fixed to the water-soluble envelope.

The terms “portion packaging” and “detergent portion” are used in the following description without excluding other inventive portion packaging where “detergent portion” is mentioned. In fact, the portion packaging is also suitable for other applications, such as pesticides, pharmaceuticals, cosmetics etc.

Firstly, the portion packaging includes a water-soluble envelope. This envelope can consist of a single material or a blend of different materials. In preferred portion packaging according to the invention, the water-soluble envelope comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and/or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, particularly MC, HEC, HPC, HPMC and/or copolymers as well as their mixtures. Optionally, well known plasticizers can be blended into the envelope in order to increase the flexibility of the material.

In the context of the present invention, polyvinyl alcohols are particularly preferred water-soluble polymers. “Polyvinyl alcohols” (abbreviation PVAL, sometimes also PVOH) is the term for polymers with the general structure

which comprise lesser amounts (ca. 2%) of structural units of the type

Typical commercial polyvinyl alcohols, which are offered as yellowish white powders or granules having degrees of polymerization in the range of approx. 100 to 2500 (molar masses of approximately 4000 to 100 000 g/mol), have degrees of hydrolysis of 98-99 or 87-89 molar % and thus still have a residual acetyl group content. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the initial polymer, the degree of hydrolysis, the saponification number and/or the solution viscosity.

The solubility in water and in a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide) of polyvinyl alcohols is a function of the degree of hydrolysis; they are not attacked by (chlorinated) hydrocarbons, esters, fats or oils. Polyvinyl alcohols are classed as toxicologically unobjectionable and are at least partially biodegradable. The solubility in water can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni salts or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are substantially impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but do allow water vapor to pass.

Preferred portion packaging in the context of the present invention are characterized in that the water-soluble envelope comprises polyvinyl alcohols and/or PVAL copolymers whose degree of hydrolysis is from 70 to 100 molar %, preferably from 80 to 90 molar %, with particular preference from 81 to 89 molar %, and in particular from 82 to 88 molar %.

Preferably, polyvinyl alcohols of a defined molecular weight range are used, wherein preferred portion packaging according to the invention are those where the water-soluble envelope comprises polyvinyl alcohols and/or PVAL copolymers, whose molecular weights lie in the range 3500 to 100 000 gmol⁻¹, preferably from 10 000 gmol⁻¹ to 90 000 gmol⁻¹, particularly preferably from 12 000 to 80.000 gmol⁻¹, and especially from 13 000 to 70 000 gmol⁻¹.

The degree of polymerization of such preferred polyvinyl alcohols lies between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, with particular preference between approximately 240 to approximately 1680, and in particular between approximately 260 to approximately 1500.

According to the invention, preferred portion packaging are characterized in that the water-soluble envelope comprises polyvinyl alcohols and/or PVAL copolymers whose average degree of polymerization lies between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and/or whose molecular weight ratio MG_((50%)) to MG_((90%)) lies between 0.3 and 1, preferably between 0.4 and 0.8 and particularly between 0.45 and 0.6.

In summary, portion packaging according to the invention are preferred in which the envelope comprises polyvinyl alcohols and/or PVAL copolymers whose hydrolysis degree amounts to 70 to 100 molar %, preferably 80 to 90 molar %, particularly preferably 81 to 89 molar % and especially 82 to 88 molar %, polyvinyl alcohols and/or PVAL copolymers being preferred whose molecular weight lies in the range 3500 to 100 000 gmol⁻¹, preferably 10 000 to 90 000 gmol⁻, particularly preferably 12 000 to 80 000 gmol⁻¹ and particularly 13 000 to 70 000 gmol⁻¹, and particularly preferred polyvinyl alcohols and/or PVAL copolymers having an average polymerization degree between 80 and 700, preferably between 150 and 400, particularly preferably between 180 to 300 and/or whose molecular weight ratio MG_((50%)) to MG_((90%)) lies between 0.3 and 1, preferably between 0.4 and 0.8 and particularly between 0.45 and 0.6.

The above-described polyvinyl alcohols are widely commercially available, for example under the trade name Mowiol® (Clariant). Examples of polyvinyl alcohols which are particularly suitable in the context of the present invention are Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, and Mowiol®8-88.

Further polyvinyl alcohols that are particularly suitable as materials for the water-soluble envelope are to be found in the following table: Degree of Molecular Melting Description Hydrolysis [%] Weight [kDa] Point [° C.] Airvol ® 205 88 15-27 230 Vinex ® 2019 88 15-27 170 Vinex ® 2144 88 44-65 205 Vinex ® 1025 99 15-27 170 Vinex ® 2025 88 25-45 192 Gohsefimer ® 5407 30-28 23.600 100 Gohsefimer ® LL02 41-51 17.700 100

Further polyvinyl alcohols that are suitable as materials for the water-soluble envelope are ELVANOL® 51-05, 52-22, 5042, 85-82, 75-15, T-25, T-66, 90-50 (trade mark of Du Pont), ALCOTEX® 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47 (trade mark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26,NM11Q, KZ-06 (trade mark of Nippon Gohsei K. K. ). ERKOL types from Wacker are also suitable.

A further preferred group of water-soluble polymers that according to the invention can serve as envelopes, are polyvinyl pyrrolidones. These are marketed, for example, under the designation Luviskol®) (BASF). Polyvinyl pyrrolidones [poly(1-vinyl-2-pyrrolidinones)], abbreviated PVP, are polymers of the general formula (I)

prepared by free-radical polymerization of 1-vinyl pyrrolidone by solution or suspension polymerization processes using free-radical initiators (peroxides, azo compounds). The ionic polymerization of the monomer yields only products with low molecular weights. Typical commercial polyvinyl pyrrolidones have molecular weights in the range of approx. 2500-750 000 g/mol, which are characterized by stating the K values and K value-dependent glass transition temperatures of 130-175° C. They are supplied as white, hygroscopic powders or as aqueous solutions. Polyvinyl pyrrolidones are readily soluble in water and a large number of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc).

Copolymers of vinyl pyrrolidones with other monomers, particularly vinyl pyrrolidone-vinyl ester copolymers, are also suitable, as marketed for example under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinyl pyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers obtainable from vinyl esters with the groups of formula (II)

as the characteristic basic structural unit of the macromolecules. Of these, the vinyl acetate polymers (R═CH₃) with polyvinyl acetates, are by far the most important representatives and have the greatest industrial significance.

The vinyl esters are polymerized free-radically by various processes (solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization).). Copolymers of vinyl acetate with vinyl pyrrolidone comprise monomer units of the formulae (I) and (II).

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are abbreviated as PEG. PEG are polymers of ethylene glycol and satisfy the general formula (III) H—(O—CH₂—CH₂)_(n)—OH   (III) wherein n can assume values between 5 and >100 000.

PEGs are industrially manufactured by the anionic ring opening polymerization of ethylene oxide (oxirane) mostly in the presence of small amounts of water. Depending on the reaction conditions, they have molecular weights in the range ca. 200-5 000 000 g/mol, corresponding to polymerization degrees of ca. 5 to >100 000.

Products with molecular weights <25 000 g/mol are liquids at room temperature and are described as true polyethylene glycols, abbreviation PEG. These short-chain PEGs can be added, especially as plasticizers, to other water-soluble polymers e.g. polyvinyl alcohols or cellulose ethers. The polyethylene glycols, which are solid at room temperature and used according to the invention, are described as polyethylene oxides, abbreviation PEOX. High molecular weight polyethylene oxides possess an extremely low concentration of reactive hydroxyl end groups and therefore show only slight properties of glycols.

According to the invention, another further suitable water-soluble coating material is gelatin, this being preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 15 000 to >250 000 g/mol) obtained principally by hydrolysis under acidic or alkaline conditions of the collagen present in the skin and bones of animals. The amino acid composition of gelatin corresponds largely to that of the collagen from which it was obtained, and varies as a function of its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in pharmacy, in the form of hard or soft gelatin capsules. Gelatin in the form of films finds only limited use, due to its high price compared with the above-cited polymers.

Further suitable water-soluble polymers for the envelope according to the invention are described below:

-   -   Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl         cellulose, and methylhydroxypropyl cellulose, as marketed for         example under the trademarks Culminal® and Benecel® (AQUALON).

Cellulose ethers may be described by the general formula (IV)

where R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is —CH₂CH₂CH₂—OH or —CH₂CH₂—OH. Cellulose ethers are prepared industrially by etherifying alkali metal cellulose (e.g., with ethylene oxide). Cellulose ethers are characterized by way of the average degree of substitution, DS, and/or by the molar degree of substitution, MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherifying reagent or how many moles of the etherifying reagent have been added on, on average, to one anhydroglucose unit. Hydroxyethyl celluloses are water-soluble above a DS of approximately 0.6 and an MS of approximately 1. Typical commercial hydroxyethyl- and hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl- and -propylcelluloses are marketed as yellowish white, odorless and tasteless powders in greatly varying degrees of polymerization. Hydroxyethyl- and -propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in the majority of (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or addition of electrolyte.

Preferred portion packaging according to the invention are characterized in that the water-soluble envelope comprises hydroxypropyl methylcellulose (HPMC), which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropyl groups per anhydroglucose unit of the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Further suitable polymers according to the invention are water-soluble amphopolymers. The generic term amphopolymers embraces amphoteric polymers, i.e., polymers whose molecule includes both free amino groups and free —COOH or SO₃H groups and are capable of forming inner salts; zwitterionic polymers whose molecule contains quaternary ammonium groups and —COO⁻ or —SO₃ ⁻ groups, and polymers containing —COOH or SO₃H groups and quaternary ammonium groups. An example of an amphopolymer which may be used in accordance with the invention is the acrylic resin obtainable under the designation Amphomer®, which constitutes a copolymer of tert-butylaminoethyl methacrylate, N-(1,1,3,3-tetramethylbutyl)acrylamide, and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g., acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids, (e.g., acrylamidopropyltrimethylammonium chloride), and, if desired, further ionic or nonionic monomers, as evident, for example, from the German laid-open specification 39 29 973 and the prior art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as available commercially under the designation Merquat® 2001 N, are particularly preferred amphopolymers in accordance with the invention. Further suitable amphoteric polymers are, for example, the octylacrylamide methyl methacrylate tert-butylaminoethyl methacrylate 2-hydroxypropyl methacrylate copolymers available under the designations Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Anionic polymers that are suitable in accordance with the invention include:

-   -   vinyl acetate-crotonic acid copolymers, as are commercialized,         for example, under the designations Resyn® (NATIONAL STARCH),         Luviset® (BASF), and Gafset® (GAF).

In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (V): [—CH(CH₃)—CH(COOH)—]_(n),   (V)

-   -   Vinyl pyrrolidone-vinyl acrylate copolymers, obtainable for         example under the trademark Luviflex® (BASF). A preferred         polymer is the vinylpyrrolidone-acrylate terpolymer obtainable         under the designation Luviflex® VBM-35 (BASF).     -   Acrylic acid ethyl acrylate N-tert-butylacrylamide terpolymers,         which are marketed for example under the designation Ultrahold®         strong (BASF).     -   Graft polymers of vinyl esters, esters of acrylic acid or         methacrylic acid alone or in a mixture, copolymerized with         crotonic acid, acrylic acid or methacrylic acid with         polyalkylene oxides and/or polyalkylene glycols Such grafted         polymers of vinyl esters, esters of acrylic acid or methacrylic         acid alone or in a mixture with other copolymerizable compounds         onto polyalkylene glycols are obtained by polymerization under         heating in a homogeneous phase, by stirring the polyalkylene         glycols into the monomers of the vinyl esters, esters of acrylic         acid or methacrylic acid, in the presence of free-radical         initiator.     -   Vinyl esters which have been found suitable are, for example,         vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate,         and those esters of acrylic acid or methacrylic acid obtainable         from low molecular weight aliphatic alcohols, i.e., in         particular, ethanol, propanol, isopropanol, 1-butanol,         2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol,         2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol,         3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol,         2-methyl-1-butanol, and 1-hexanol.

Polypropylene glycols (abbreviation PPG) are polymers of propylene glycol which satisfy the general formula VI

in which n may adopt values between 1 (propylene glycol) and several thousand. In this case the industrially significant representatives are, in particular, di-, tri- and tetrapropylene glycol, i.e., the representatives where n=2,3 and 4 in formula VI.

In particular, vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used

-   -   grafted and crosslinked copolymers from the copolymerization of         -   i) at least one monomer of the nonionic type,         -   ii) at least one monomer of the ionic type,         -   iii) polyethylene glycol, and         -   iv) a crosslinker

The polyethylene glycol used has a molecular weight of between 200 and several million, preferably between 300 and 30 000.

The nonionic monomers may be of very different types, and include the following preferred monomers: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether, and 1-hexene.

The nonionic monomers may equally be of very different types, among which particular preference is given to the presence in the graft polymers of crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid, and methacrylic acid.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para divinylbenzene, tetraallyloxyethane, and polyallylsaccharoses containing 2 to 5 allyl groups per molecule of saccharin.

The above described grafted and crosslinked copolymers are formed preferably of:

-   -   i) from 5 to 85% by weight of at least one monomer of the         nonionic type,     -   ii) from 3 to 80% by weight of at least one monomer of the ionic         type,     -   iii) 2 to 50% by weight, preferably 5 to 30% by weight, of         polyethylene glycol, and     -   iv) 0.1 to 8% by weight of a crosslinker, the percentage of the         crosslinker being defined by the ratio of the overall weights of         i), ii) and iii).     -   copolymers obtained by copolymerizing at least one monomer from         each of the three following groups:         -   i) esters of unsaturated alcohols and short-chain saturated             carboxylic acids and/or esters of short-chain saturated             alcohols and unsaturated carboxylic acids,         -   ii) unsaturated carboxylic acids,         -   iii) esters of long-chain carboxylic acids and unsaturated             alcohols and/or esters of the carboxylic acids of group ii)             with saturated or unsaturated, straight-chain or branched             C₈₋₁₈ alcohols

Short-chain carboxylic acids and alcohols here are those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if desired, by divalent hetero-groups such as —O—, —NH—, and —S—.

-   -   terpolymers of crotonic acid, vinyl acetate, and an allyl or         methallyl ester These terpolymers contain monomer units of the         general formula (II) and (IV) (see above) and monomer units from         one or more allyl or methallyl esters of formula VII:         in which R³ is —H or —CH₃, R² is —CH₃ or —CH(CH₃)₂ and R¹ is         —CH₃ or a saturated straight-chain or branched C₁₋₆ alkyl         radical and the sum of the carbon atoms in the radicals R¹ and         R² is preferably 7, 6, 5, 4, 3 or 2.

The abovementioned terpolymers result preferably from the copolymerization of from 7 to 12% by weight of crotonic acid, from 65 to 86% by weight, preferably from 71 to 83% by weight, of vinyl acetate and from 8 to 20% by weight, preferably from 10 to 17% by weight, of allyl or methallyl esters of the formula VII.

-   -   tetra- and pentapolymers of         -   i) crotonic acid or allyloxyacetic acid         -   ii) vinyl acetate or vinyl propionate         -   iii) branched allyl or methallyl esters         -   iv) vinyl ethers, vinyl esters or straight chain allyl or             methallyl esters     -   crotonic acid copolymers with one or more monomers from the         group consisting of ethylene, vinylbenzene, vinyl methyl ether,         acrylamide and the water-soluble salts thereof     -   terpolymers of vinyl acetate, crotonic acid and vinyl esters of         a saturated aliphatic α-branched monocarboxylic acid.

Further preferred polymers, which may be used according to the invention as coatings are cationic polymers. Among the cationic polymers, the permanently cationic polymers are preferred. “Permanently cationic” refers according to the invention to those polymers, which independently of pH, have a cationic group. These are generally polymers, which contain a quaternary nitrogen atom, in the form of an ammonium group, for example.

Examples of preferred cationic polymers are

-   -   quaternized cellulose derivatives, as available commercially         under the designations Celquat® and Polymer JR®. The compounds         Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are preferred         quaternized cellulose derivatives.     -   Polysiloxanes with quaternary groups, such as, for example, the         commercially available products Q2-7224 (manufacturer: Dow         Corning; a stabilized trimethylsilylamodimethicone), Dow         Corning® 929 emulsion (comprising a hydroxylamino-modified         silicone, also referred to as amodimethicone), SM-2059         (manufacturer: General Electric), SLM-55067 (manufacturer:         Wacker), and Abil®-Quat 3270 and 3272 (manufacturer: Th.         Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),     -   Cationic guar derivatives, such as in particular the products         marketed under the trade names Cosmedia® Guar and Jaguar®,     -   Polymeric dimethyldiallylammonium salts and their copolymers         with esters and amides of acrylic acid and methacrylic acid. The         products available commercially under the designations Merquat®         100 (poly(dimethyldiallylammonium chloride)) and Merquat® 550         (dimethyldiallylammonium chloride-acrylamide copolymer) are         examples of such cationic polymers.     -   Copolymers of vinyl pyrrolidone with quaternized derivatives of         dialkylamino acrylate and methacrylate, such as, for example,         vinyl pyrrolidone-dimethylamino methacrylate copolymers         quaternized with diethyl sulfate. Such compounds are available         commercially under the designations Gafquat® 734 and Gafquat®         755.     -   Vinyl pyrrolidone-methoimidazolinium chloride copolymers, as         offered under the designation Luviquat®.     -   Quaternized polyvinyl alcohol         and also the polymers known under the designations     -   Polyquaternium 2,     -   Polyquaternium 17,     -   Polyquaternium 18 and     -   Polyquaternium 27         having quaternary nitrogen atoms in the polymer main chain.         These polymers are designated in accordance with the INCI         nomenclature; detailed information can be found in the CTFA         International Cosmetic Ingredient Dictionary and Handbook, 5th         Edition, The Cosmetic, Toiletry and Fragrance Association,         Washington, 1997, expressly incorporated herein by reference.

Preferred cationic polymers in accordance with the invention are quaternized cellulose derivatives and also polymeric dimethyldiallylammonium salts and copolymers thereof. Cationic cellulose derivatives, especially the commercial product Polymer® JR 400, are especially preferred cationic polymers.

The envelope of the detergent portions according to the invention can comprise, in addition to the water-soluble polymer and/or the water-soluble polymers, further constituents, which especially improve the processability of the envelope starting materials. These are particularly plasticizers and mold release agents. Moreover, colorants and/or perfumes and optical brighteners can be incorporated into the water-soluble envelope to realize aesthetic and/or technical effects therein.

In particular, hydrophilic, high-boiling liquids may be used according to the invention as plasticizers, materials that are solid at room temperature also being used in the form of solutions, dispersions or melts, when needed. Particularly preferred plasticizers come from the group glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythreitol, mono-, di-, triglycerides, surfactants, especially nonionic surfactants and mixtures thereof.

Ethylene glycol (1,2-ethanediol, “glycol”) is a colorless, viscous, sweet tasting, strongly hygroscopic liquid that is miscible with water, alcohols and acetone, and has a density of 1.113. The freezing point of ethylene glycol is at −11.5° C., the liquid boils at 198° C. Ethylene glycol is obtained industrially by heating ethylene oxide with water under pressure. Promising manufacturing processes can be based on the acetoxylation of ethylene and subsequent hydrolysis or on syngas reactions.

Diethylene glycol (2,2′-oxydiethanol, digol), HO—(CH₂)₂—O—(CH₂)₂—OH, is a colorless, viscous, hygroscopic, sweet tasting liquid, density 1.12 melting at −6° C. and boiling at 245° C. Diglycol is miscible in all proportions with water, alcohols, glycol ethers, ketones, chloroform, but not with hydrocarbons or oils. Diethylene glycol, mostly known in the trade as simply diglycol, is manufactured from ethylene oxide and ethylene glycol (ethoxylation) and is therefore practically the initial member of the polyethylene glycols (see above).

Glycerin is a colorless, clear, highly viscous, odorless, sweet tasting, hygroscopic liquid, density 1.261, which solidifies at 18.2° C. Originally, glycerin was only a by-product of fat saponification, but is now synthesized industrially in large quantities. Most industrial processes are based on propylene, which is converted to glycerin via the intermediates allyl chloride, epichlorohydrin. A further industrial process is the hydroxylation of allyl alcohol over WO₃ with hydrogen peroxide via glycid.

Trimethylol propane [TMP, etriol, ettriol, 1,1,1-tris(hydroxymethyl)propane] chemically correctly described as 2-ethyl-2-hydroxymethyl-1,3-propanediol, is commercially available as a colorless, hygroscopic substance with a melting point of 57-59° C. and a boiling point of 160° C. (7 hPa). It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. It is manufactured by the reaction of formaldehyde with butyraldehyde in the presence of alkalies.

Pentaerythreitol [2,2-bis(hydroxymethyl)-1,3-propanediol, Penta, PE] is a white, crystalline powder with a sweet taste and is neither hygroscopic nor inflammable, density 1.399, melting point 262° C. and boiling point 276° C. (40 hPa). Pentaerythreitol has good solubility in boiling water, is weakly soluble in alcohol, and insoluble in benzene, tetrachloromethane, ether, petroleum ether. Pentaerythreitol is manufactured industrially by reacting formaldehyde with acetaldehyde in an aqueous solution of Ca (OH)₂ or NaOH at 15-45° C. The reaction takes place initially as an aldol reaction, whereby the formaldehyde reacts as the carbonyl component and the acetaldehyde as the methylene component. Due to the high carbonyl activity of the formaldehyde, the reaction of acetaldehyde with itself hardly occurs. Finally, the tris(hydroxymethyl)acetaldehyde undergoes a crossed Cannizzaro reaction with formaldehyde to afford pentaerythreitol and formate.

Mono-, di-, triglycerides are esters of fatty acids, preferably long chain fatty acids with gylcerin, wherein according to the glyceride type, one two or three OH groups are esterified. Acid components that can be esterified with glycerin to form mono-, di- or triglycerides as suitable plasticizers according to the invention, are, for example hexanoic acid (capronic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (caprinic acid), undecanoic acid etc. In the context of the present invention, preferred, suitable fatty acids are dodecanoic acid (laurinic acid), tetradecanoic acid (myristinic acid), hexadecanoic acid (palmitinic acid), octadecanoic acid (stearinic acid), eicosanoic acid (arachinic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignocerinic acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissinic acid) as well as the unsaturated series 9c-hexadecenoic acid (palmitoleinic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (olic acid), 9t-octadecenoic acid (elaidinic acid), 9c,12c-octadecadienoic acid (linolic acid), 9t,12t-octadecadienoic acid (linolaidinic acid) and 9c,12c,15c-octadecatrienoic acid (linolenic acid). On the grounds of cost, natural fats (triglycerides) or modified natural fats (partially hydrolyzed oils and fats) can also be used directly. Alternatively, mixtures of fatty acids can be manufactured by cleaving natural fats, separated in a subsequent step, the purified fractions being reacted once more to afford mono-, di- and triglycerides. Acids that are esterified with glycerin are particularly coconut oil fatty acid (about 6% by weight C8, 6% by weight C10, 48% by weight C12, 18% by weight C14, 10% by weight C16, 2% by weight C18, 8% by weight C18′, 1% by weight C18″), palm kernel oil fatty acid (about 4% by weight C8, 5% by weight C10, 50% by weight C12, 15% by weight C14, 7% by weight C16, 2% by weight C18, 15% by weight C18′, 1% by weight C18″), tallow fatty acid (about 3% by weight C14, 26% by weight C16, 2% by weight C16′, 2% by weight C17, 17% by weight C18, 44% by weight C18′, 3% by weight C18″, 1% by weight C18′″), hydrogenated tallow fatty acid (about 2% by weight C14, 28% by weight C16, 2% by weight C17, 63% by weight C18, 1% by weight C18′), technical-grade oleic acid (about 1% by weight C12, 3% by weight C14, 5% by weight C16, 6% by weight C16′, 1% by weight C17, 2% by weight C18, 70% by weight C18′, 10% by weight C18″, 0.5% by weight C18′″), technical-grade palmitic/stearic acid (about 1% by weight C12, 2% by weight C14, 45% by weight C16, 2% by weight C17, 47% by weight C18, 1% by weight C18′), and soybean oil fatty acid (about 2% by weight C14, 15% by weight C16, 5% by weight C18, 25% by weight C18′, 45% by weight C18″, 7% by weight C18′″).

Surfactants, particularly nonionic surfactants can also be considered for use as additional plasticizers. Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, particularly primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates with linear groups of alcohols of natural origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C₁₂₋ ₁₄ alcohols with 3 EO or 4 EO, C₉₋₁₁ alcohol with 7 EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂₋₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C₁₂₋₁₄- alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5 EO. The degrees of ethoxylation mentioned represent statistical mean values, which, for a special product, can be a whole number or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used, examples including tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants that have a melting point above room temperature are used with particular preference as plasticizers. Accordingly, preferred envelopes are characterized in that nonionic surfactant(s) with a melting point above 20° C., preferably above 25° C., particularly preferably between 25 and 60° C. and, especially between 26.6 and 43.3° C. are used as plasticizers.

Suitable nonionic surfactants with a melting and/or softening point in the cited temperature range are, for example weakly foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonioriic surfactants are used that are highly viscous at room temperature, they preferably have a viscosity above 20 Pas, particularly preferably above 35 Pas and especially above 40 Pas. Nonionic surfactants, which are wax-like in consistency at room temperature, are also preferred.

Preferred nonionic surfactants that are solid at room temperature are used and belong to the groups of alkoxylated nonionic surfactants, more particularly ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants.

In one preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant that results from the reaction of a monohydroxyalkanol or alkylphenol containing 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles and especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred nonionic surfactant that is solid at room temperature is obtained from a straight-chain fatty alcohol containing 16 to 20 carbon atoms (C₁₆₋₂₀ alcohol), preferably a C₁₈ alcohol, and at least 12 moles, preferably at least 15 moles and more preferably at least 20 moles of ethylene oxide. Of these nonionic surfactants, the so-called narrow range ethoxylates (see above) are particularly preferred.

Accordingly, ethoxylated non-ionic surfactant(s) is/are used in particularly preferred processes according to the invention, which is/are prepared from C₆₋₂₀-monohydroxyalkanols or C₆₋₂₀-alkylphenols or C₁₆₋₂₀-fatty alcohols and more than 12 mole, preferably more than 12 mole and especially more than 20 mole ethylene oxide per mole alcohol.

The nonionic surfactant preferably contains additional propylene oxide units in the molecule. These PO units preferably make up as much as 25% by weight, more preferably as much as 20% by weight and, especially up to 15% by weight of the total molecular weight of the nonionic surfactant.

Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which have additional polyoxyethylene-polyoxypropylene block copolymer units.

The alcohol or alkylphenol component of these nonionic surfactant molecules preferably makes up more than 30 wt. %, more preferably more than 50 wt. % and most preferably more than 70 wt. % of the total molecular weight of these nonionic surfactants.

Other particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend that contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Further preferred nonionic surfactants satisfy the formula R¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)[CH₂CH(OH)R²]. in which R¹ stands for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R². means a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

Further preferred suitable nonionic surfactants are the end group blocked poly(oxyalkylated) nonionic surfactants of the formula R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR² in which R¹ and R² stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R³ stands for H or for a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x has a value between 1 and 30, k and j have values between 1 and 12, preferably between 1 and 5. Where x has a value of >2, each substituent R³ in the above formula may be different. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals containing 6 to 22 carbon atoms, radicals containing 8 to 18 carbon atoms being particularly preferred. H, —CH3 or —CH₂CH₃ are particularly preferred for the radical R³ Particularly preferred values for x are in the range from 1 to 20 and more particularly in the range from 6 to 15.

As described above, each R³ in the above formula can be different for the case where x≧2. By this means, the alkylene oxide unit in the straight brackets can be varied. If, for example, x has a value of 3, the substituent R³ may be selected to form ethylene oxide (R³═H) or propylene oxide (R³═CH₃) units which may be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x was selected by way of example and may easily be larger, the range of variation increasing with increasing x-values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups or vice versa.

Particularly preferred endblocked poly(oxyalkylated) alcohols of the above formula have values k=1 and j=1, such that the above formula is simplified to R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

In this last formula, R¹, R² und R³ are as defined above and x stands for a number from 1 to 30, preferably 1 to 20 and especially 6 to 18. Surfactants in which the substituents R¹ and R² have 9 to 14 carbon atoms, R³ stands for H and x takes a value of 6 to 15 are particularly preferred.

Further preferred substances for use as plasticizers can be glycerin carbonate, propylene glycol and propylene carbonate.

Glycerin carbonate is obtained by the transesterification of ethylene carbonate or dimethyl carbonate with glycerin, producing ethylene glycol or methanol as by-products. A further synthesis starts with gycidol (2,3-epoxy-1-propanol), which is reacted under pressure with CO₂ in the presence of catalysts to form glycerin carbonate. Glycerin carbonate is a clear liquid of low viscosity with a density of 1.398 g.cm⁻³ that boils at 125-130° C. (0.15 mbar).

Two isomers of propylene glycol exist, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol(trimethylene glycol) is a neutral, colorless and odorless, sweet tasting liquid, density 1.0597, solidifying at −32° C. and boiling at 214° C. 1,3-propanediol is manufactured from acrolein and water followed by catalytic hydrogenation.

By far the more industrially important 1,2-propanediol(propylene glycol) is an oily, colorless, almost odorless liquid, density 1.0381, solidifying at −60° C. and boiling at 188° C. 1,2-propanediol is manufactured by adding water to propylene oxide.

Propylene carbonate is a water-white liquid of low viscosity with a density of 1.21 gcm⁻³, melting point −49° C., boiling point 242° C. Propylene carbonate is also industrially manufactured from propylene oxide by the reaction of CO₂ at 200° C. under 80 bar.

Highly dispersed silicic acids are particularly suitable as further additives, which are preferably solid at room temperature. Pyrogenic silicic acids such as commercial Aerosil® or precipitated silicic acids are available. Particularly preferred processes according to the invention are characterized in that one or more materials from the group (preferably highly dispersed) silicic acid, dispersion powder, high molecular weight polyglycols, stearic acid and/or stearic acid salts, and from the group of inorganic salts like sodium sulfate, calcium chloride and/or from the group of inclusion hosts such as urea, cyclodextrin and/or from the group superadsorbers like (preferably crosslinked) polyacrylic acid and/or their salts like Cabloc 5066/CTF and their mixtures is/are used as additional additives.

The water-soluble envelope can be obtained from the above materials and/or their mixtures by injection- or blow molding processes. The molding can be made both from the melt and also from a solution with subsequent drying. Other methods of molding in plastic processing are also suitable. On the grounds of process economics, it is preferred that the water-soluble envelope of the portion packaging according to the invention is formed from a film material whose thickness ranges from 10 to 1000 μm, preferably 20 to 750 μm and especially 30 to 500 μm.

The portion packaging according to the invention comprise an additional constituent, a “core”—i.e. a solid, which markedly differentiates itself in its size from the particle compositions. Preferred cores have, for example a minimum diameter greater than 2 mm, wherein preferred cores have a weight greater than 200 mg, particularly preferably greater than 500 mg and especially greater than 1 g.

Cores can be manufactured using typical manufacturing processes for solids, preferably by tabletting. Portion packaging according to the invention are preferred in which the core is a tablet. Cores can be tabletted using all current tablet molds and types, so that two-layer cores with different layer compositions can also be manufactured, for example.

Alternatively, cores can also be manufactured by casting and subsequent solidification. Portion packaging according to the invention are preferred here, in which the core is a solidified melt. Of course, no limits are set to the creativity of the product designer, and thus cores, which are combinations of tabletted constituents and, when required, of cast parts, are also utilizable according to the invention.

Should it be desirable from material, technical manufacturing or aesthetic grounds to process liquids, then cores can also be incorporated, which contain liquid in an envelope. Besides injection molded or blow molded parts, gelatin capsules can be especially considered.

According to the invention, the portion packaging comprises at least one core. In the following description, it is not always explicitly stated that the packaging can also comprise a plurality of cores. The use of the singular in the following illustration is not to be understood as limiting.

According to the invention, the core is fixed to the water-soluble envelope. In addition to being fixed, the core can be surrounded by walls or means that form compartments in such a way that it is delimited from at least one zone of the water-soluble envelope. This procedure creates a plurality of compartments, in which mutually incompatible constituents can be present without any reaction between them. Accordingly, packaging according to the invention, in which the core is sterically delimited by means of an internal partition wall or a weir, are preferred.

The core or cores can be fixed by various methods. For example, it is possible to create a form fit or a squeeze fit between the water-soluble envelope and the core. A possibility exists here that the core is fixed to the water-soluble envelope by positioning the core in a shaped cavity of the envelope.

For reasons of process economics, it may be preferred to drop the core into a hollow in the envelope, such that it penetrates into the hollow through its own weight. Adherence in such a hollow can then be advantageously provided by shrinking the envelope material around the core and thus locking it in. Because of the less expensive mechanical core dosing, this type of fixing is preferred over the previous method. Accordingly, portion packaging according to the invention are preferred in which the core is fixed to the water-soluble envelope by shrunk-back envelope material.

As an alternative to the form fit or shape fit, or as a complement to them, the core can also be fastened to the envelope by adhesion fitting. Here, portion packaging according to the invention are preferred in which the core is fixed to the water-soluble envelope by an adhesive bonding.

The adhesive bonding can be produced, for example, by moistening the water-soluble packaging at the place where the core is inserted. By this the water-soluble envelope is partially dissolved, creating a highly concentrated polymer solution almost in situ, which can serve as an adhesion promoter. Naturally, other adhesion promoters can also be used.

Preferred materials for the adhesive bonding are adhesives or so-called adhesion promoters. Thus, in the context of the present invention, solutions, dispersions, emulsions or melts having a viscosity below 3000 mPas, are preferred as adhesion promoters.

In the context of the present invention, the viscosity values refer to viscosity measurements at a sample temperature, which corresponds to a processing temperature of the adhesion promoter(s) (see below), using a Carrimed plate-plate rheometer at a shear force of 50 N per square meter, a plate diameter of 5 cm and a measuring slit of 250 μm, the value being read after 10 seconds measuring time.

During processing, preferred adhesion promoters have a viscosity below 2500 mPas, preferably below 2000 mPas and especially below 1000 mPas.

The processing temperature of the adhesion promoter(s) depends on the material nature of the adhesion promoter used and the desire time in which the adhesion promoter should develop its adhesion. In this respect, temperatures ranging from room temperature (which in winter months can sometimes be between 10 and 15° C.) up to high temperature above the boiling point of water are feasible. In preferred methods of preparing adhesive bonds in the context of the present invention, the adhesion promoters are added into the cavity at a temperature between 10 and 130° C., preferably between 20 and 110° C. and especially between 20 and 90° C.

The adhesion promoter(s) can be added as a melt, which normally can require temperatures above 30° C., preferably above 40° C. and especially above 50° C.

In the context of the present invention, particularly preferred meltable adhesion promoters are substances from the group of polyethylene- and polypropylene glycols. Also, mixtures of substances that comprise these materials are preferred. Accordingly, added adhesion promoters from the group of polyethylene glycols (PEG) and/or polypropylene glycols (PPG) are preferred embodiments of the present invention.

According to the invention, suitable polyethylene glycols (abb. PEG) are polymers of ethylene glycol with the general formula H—(O—CH₂—CH₂)_(n)—OH wherein n can take values between 1 (ethylene glycol) and over 100 000. The viscosity of the PEG at the processing temperature is a critical factor in evaluating whether a polyethylene glycol may be used according to the invention. As the preferred process is carried out above 20° C. and below 90° C., those polyethylene glycols of the above formula are especially suitable when the n value is between ca. 15 and ca. 150. High molecular weight polyethylene glycols are polymolecular, i.e. they consist of groups of macromolecules with different molecular weights. Various nomenclatures are used for polyethylene glycols, which can lead to confusion. It is common practice to indicate the mean relative molecular weight after the initials “PEG”, so that “PEG 200” characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. Under this nomenclature, the standard polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 may advantageously be used for the purposes of the present invention.

Cosmetic ingredients are covered by another nomenclature in which the initials PEG are followed by a hyphen and the hyphen is in turn directly followed by a number which corresponds to the index n in the above formula. Under this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), PEG-32, PEG40, PEG-55, PEG-60, PEG-75 and PEG-100, for example, may advantageously be used in accordance with the present invention.

Polyethylene glycols are commercially obtainable, for example under the-trade names of Carbowax® PEG 540 (Union Carbide), Emkapol® 2000 (ICI Americas), Lipoxol® 2000 MED (HULS America), Polyglycol®EE-1550 (Dow Chemical), Lutrol® E2000 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (abb. PPG) suitable for use in accordance with the invention are polymers of propylene glycol which correspond to general formula

wherein n can take values between 1 (propylene glycol) and about 1000. As with the PEGs described above, a critical factor in evaluating whether a polypropylene glycol is suitable for use in accordance with the invention is the viscosity of the PPG, at the processing temperature.

In the context of the present invention, the standard polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 may advantageously be used.

As the temperature control for the addition of melts can be critical, it is preferred, according to the invention, to use solutions or dispersions of adhesion promoters, which are solid at room temperature, and/or emulsions of adhesion promoters, which are liquid at room temperature. In this context, the emulsions are of only minor importance, because of occasional problems encountered concerning adhesion of the core. Dispersions, because of problems with precipitation during processing, are also less suitable than the particularly preferred solutions.

Particularly preferred adhesion promoters are solutions of defined nonionic materials. Preferred adhesion promoters are solutions of polyhydroxy alcohols and/or sugars that are solid at room temperature, solutions being preferred which comprise at least 30 wt. %, preferably at least 40 wt. % and especially at least 50 wt. % solid(s), based on the solution.

In the context of the present invention, polyhydroxy alcohols are compounds that contain at least two hydroxyl groups. The physical state of these compounds at room temperature (20° C.) is solid. Particularly preferred polyhydroxy alcohols are, for example trimethylolpropane, pentaerythreitol as well as “sugar alcohols” i.e. polyhydroxy alcohols obtained by reducing the carbonyl groups of monosaccharides. They are differentiated according to the number of hydroxyl groups in the molecule tetrite, pentite, hexite etc. In the context of the present invention, particularly preferred sugar alcohols are e.g. threitol and erythritol, adonitol (ribitol) arabitol (previously lyxitol) and xylitol, dulcitol (galactitol), mannitol and sorbitol (glucitol), the last being also known as sorbitol.

For the purposes of the present invention, the term “sugar” signifies simple sugars and polysugars, i.e. monosaccharides and oligosaccharides in which 2 to 6 monosaccharides are joined together in the form of an acetal. For the purposes of the present invention, “sugars” are thus monosaccharides, disaccharides, trisaccharides, tetrasaccharides, pentasaccharides and hexasaccharides.

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (ketoses). They mostly have a chain length of five (pentoses) or six (hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses etc.) or fewer (tetroses) carbon atoms are relatively rare. Some monosaccharides have a large number of asymmetric carbon atoms. For a hexose having four asymmetric carbon atoms, there are 24 stereoisomers in total. The orientation of the OH group on the highest-numbered asymmetric carbon atom in the Fischer projection divides the monosaccharides into D- and L-configured series. In the case of the naturally occurring monosaccharides, the D-configuration is considerably more common. Monosaccharides form, where possible, intramolecular hemiacetals, giving ring structures of the pyran (pyranoses) and furan type (furanoses). Smaller rings are unstable, and larger rings are only stable in aqueous solutions. Cyclization produces a further asymmetrical carbon atom (the so-called anomeric carbon atom), which again doubles the number of possible stereoisomers. This is expressed by the prefixes α- and β-. The formation of the hemiacetals is a dynamic process, which depends on a variety of factors, such as temperature, solvents, pH etc. In most cases, mixtures of the two anomeric forms are present, sometimes also as mixtures of the furanose and pyranose forms.

Monosaccharides which can be used for the purposes of the present invention are, for example, the tetroses D(−)-erythrose and D(−)-threose, and D(−)-erythrulose, the pentoses D(−)-ribose, D(−)-ribulose, D(−)-arabinose, D(+)-xylose, D(−)-xylulose, and D(−)-lyxose and the hexoses D(+)-allose, D(+)-altrose, D(+)-glucose, D(+)-mannose, D(−)-gulose, D(−)-idose, D(+)-galactose, D(+)-talose, D(+)-psicose, D(−)-fructose, D(+)-sorbose and D(−)-tagatose. The most important and most widespread monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose and 2-deoxy-D-ribose.

Disaccharides are constructed of two simple monosaccharide molecules (D-glucose, D-fructose etc.) linked by a glycosidic bond. If the glycosidic bond is between the acetalic carbon atoms (1 in the case of aldoses and 2 in the case of ketoses) of the two monosaccharides, then the ring form is fixed therewith for both; the sugars do not exhibit mutarotation, do not react with ketone reagents and no longer have a reducing action (Fehling negative: trehalose or sucrose type). By contrast, if the glycosidic bond links the acetalic carbon atom of a monosaccharide with any of the second, then this can also assume the open-chain form, and the sugar still has a reducing action (Fehling positive: maltose type).

The most important disaccharides are sucrose (raw sugar, saccharose), trehalose, lactose (milk sugar), lactulose, maltose (malt sugar), cellobiose (degradation product of cellulose), gentobiose, melibiose, turanose and others.

Trisaccharides are carbohydrates constructed of 3 monosaccharides linked together glycosidically and which are sometimes also incorrectly referred to as trioses. Trisaccharides occur relatively seldomly in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, and as an example of trisaccharides containing amino sugars, streptomycin and validamycin.

Tetrasaccharides are oligosaccharides having 4 monosaccharide units. Examples of this class of compound are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (comprising 4 fructose units).

For the purposes of the present invention, preferred sugars are saccharides from the group glucose, fructose, sucrose, cellobiose, maltose, lactose, lactulose, ribose and mixtures thereof. Particularly preferred detergent shaped bodies comprise glucose and/or sucrose.

A preferred adhesion promoter used in the form of a solution is sorbitol. Here, processes according to the invention are preferred in which adhesion promoters are solutions of sorbitol, which comprise at least 50 wt. %, preferably at least 60 wt. % and especially at least 70 wt. % sorbitol, based on the solution.

A further preferred class of materials, which can be used in the form of a solution, are water-soluble polyurethanes. Specific representatives of these are particularly preferred. Here, processes according to the invention are preferred in which the adhesion promoters are used as solutions or suspensions of polyurethanes of diisocyanates (A) and diols (B) O═C═N—R¹—N═C═O   (A), H—O—R²—O—H   (B), wherein the diols are at least partially selected from polyethylene glycols (a) and/or polypropylene glycols (b)

and R¹ an R², independently of one another stand for a substituted or unsubstituted, straight chain or branched alkyl, aryl or alkylaryl radical with 1 to 24 carbon atoms and each n stands for 5 to 2000.

These preferred polymers are described in more detail in the following.

Polyurethanes are polyadducts of at least two different types of monomer,

-   -   a di- or polyisocyanate (A) and     -   a compound (B) having at least 2 active hydrogen atoms per         molecule.

The polyurethanes, which can be used in the solution or suspension or dispersion are obtained from reaction mixtures, which comprise at least one diisocyanate of the formula (A) and at least one polyethylene glycol of the formula (a) and/or at least one polypropylene glycol of the formula (b).

In addition, the reaction mixtures may comprise further polyisocyanates. Also possible is the presence in the reaction mixtures—and hence in the polyurethanes—of other diols, triols, diamines, triamines, polyetherols and polyesterols. The compounds having more than 2 active hydrogen atoms are normally used in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.

Where further diols, etc., are added, it is necessary to observe particular proportions in relation to the polyethylene- and/or polypropylene glycol units that may be present in the polyurethane. Preference is given here when at least 10% by weight, preferably at least 25% by weight, with particular preference at least 50% by weight, and in particular, at least 75% by weight of the diols incorporated into the polyurethane by reaction are selected from polyethylene glycols (a) and/or polypropylene glycols (b).

In addition to the special polyurethanes, the solution or dispersion or suspension of the adhesion promoter can comprise further constituents, such as detergent constituents, in particular colorants and/or perfumes.

The polyurethanes contain, as monomer unit, diisocyanates of the formula (AA). Diisocyanates used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4′,-methylene di(phenyl isocyanate) and, in particular, isophorone diisocyanate. These compounds can be described by the formula (A) given above in which R1 is a connecting group of carbon atoms, for example, a methylene, ethylene, propylene, butylene, pentylene, hexylene, etc., group. In the above mentioned hexamethylene diisocyanate (HMDI), which is the one generally used in industry, it is the case that R¹═(CH₂)₆; in 2,4- and 2,6-toluene diisocyanate (TDI) R¹ is C₆H₃—CH₃), in 4,4′-methylenedi(phenyl isocyanate) (MDI) it is C₆H₄—CH₂—C₆H₄), and in isophorone diisocyanate R¹ stands for the isophorone radical (3,5,5-trimethyl-2-cyclohexenone).

The polyurethanes contain, as a monomer unit, additional diols of the formula (B), these diols originating at least partly from the group of the polyethylene glycols (a) and/or of the polypropylene glycols (b). Polyethylene glycols are polymers of ethylene glycol which satisfy the general formula (a) H—(O—CH₂—CH₂)_(n)—OH   (a) (see above).

Polypropylene glycols (abb. PPG) are polymers of propylene glycol which correspond to general formula (b)

wherein n can take values between 5 and 2000.

Both for cases of compounds of formula (a) and for compounds of formula (b), preferred monomers are those representatives for which the number n stands for a number between 6 and 1500, preferably, between 7 and 1200, particularly preferably between 8 and 1000, further preferred between 9 and 500 and especially between 10 and 200. For specific applications, polyethylene- and polypropylene glycols of formulae (IIa) and/or (IIb) can be preferred, in which n stands for a number between 15 and 150, preferably, between 20 and 100, particularly preferably between 25 and 75 and especially between 30 and 60.

Examples of further compounds optionally contained in the reaction mixtures for the preparation of polyurethanes are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α,ω-diamines based on long chain alkanes or polyalkylene oxides. Detergent molded bodies, in which the polyurethanes in the coating comprise additional diamines, preferably hexamethylenediamine and/or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred

According to which reaction partners react together to form the polyurethanes, polymers are obtained with different structural units. Here, processes according to the invention are preferred in which solutions or suspensions of polyurethanes are used that comprise structural units of formula (C) —[O—C(O)—NH—R¹—NH—C(O)—O—R²]_(k)—  (C), in which R¹ stands for —(CH₂)₆— or for 2,4- or 2,6-C₆H₃—CH₃, or for C₆H₄—CH₂—C₆H₄ and R2 is selected from —CH₂—CH₂—(O—CH₂—CH₂)_(n)— or —CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(n)—, wherein n is a number from 5 to 199 and k is a number from 1 to 2000.

In this context it is possible for the preferred described diisocyanates to be reacted with all of the preferred described diols, to give polyurethanes; consequently, in preferred processes according to the invention, polyurethanes, which possess one or more of the structural units (C a) to (C h) are used: —[O—C(O)—NH—(CH₂)₆—NH—C(O)—O—CH₂—CH₂—(O—CH₂—CH₂)_(n)]_(k)—  (C a), —[O—C(O)—NH-(2,4-C₆H₃—CH₃)—NH—C(O)—O—CH₂—CH₂—(O—CH₂—CH₂)_(n)]_(k)—  (C b), —[O—C(O)—NH-(2,6-C₆H₂—CH₃)—NH—C(O)—O—CH₂—CH₂—(O—CH₂—CH₂)_(n)]_(k)—  (C c), —[O—C(O)—NH—(C₆H₄—CH₂—H₄)—NH—C(O)—O—CH₂—CH₂—(O—CH₂—CH₂)_(n)]_(k)—  (C d), —[O—C(O)—NH—(CH₂)₆—NH—C(O)—O—CH(CH₃)-CH₂—(O—CH(CH₃)—CH₂)_(n)]_(k)—  (C e), —[O—C(O)—NH-(2,4-C₆H₃—CH₃)—NH—C(O)—O—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(n)]_(k)—  (C f), —[O—C(O)—NH-(2,6-C₆H₃—CH₃)—NH—C(O)—O—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(n)]_(k)—  (C g), —[O—C(O)—NH—(C₆H₄—CH₂—C₆H₄)—NH—C(O)—O—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(n)]_(k)—  (C h) where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, besides diisocyanates (A) and diols (B), the reaction mixtures may also include further compounds from the group of the polyisocyanates (especially triisocyanates and tetraisocyanates) and also from the group of polyols and/or di- and/or polyamines. In particular, triols, tetrols, pentols, and hexols, and diamines and triamines, may be present in the reaction mixtures. The presence of compounds having more than two “active” hydrogen atoms (all aforementioned classes of substance except for the diamines) leads to partial crosslinking of the polyurethane reaction products and may give rise to advantageous properties such as, for example, control of dissolution behavior, stability or flexibility of the adhesive bond, process advantages when metering etc. The amount of such compounds having more than two “active” hydrogen atoms in the reaction mixture is normally less than 20% by weight of the reactants employed overall for the diisocyanates, preferably less than 15% by weight, and in particular less than 5% by weight.

In preferred embodiments of the present invention the polyurethanes in the coating possess molecular weights from 5000 to 150 000 gmol⁻¹, preferably from 10 000 to 100 000 g mol⁻¹, and in particular from 20 000 to 50 000 gmol⁻¹.

A third constituent of the portion packaging according to the invention is a matrix of free-flowing material, which is contained in the envelope, and at least partially surrounds the core(s). In the context of the present invention, “free-flowing” means that the matrix can be brought into the envelope by a simple dosing process. The term “free-flowing” thereby expressly encompasses the terms “conveyable” and/or “pourable”.

In preferred embodiments of the present invention, the free-flowing material is a liquid or a free-flowing gel. Here, portion packaging according to the invention are preferred in which the free-flowing material is a liquid, whose viscosity (Brookfield-Viscosimeter LVT-II at 20 rpm and 20° C., spindle 3) lies preferably in the range from 500 to 50 000 mPas, further preferred from 1000 to 10 000 mPas, especially preferred from 1200 to 5000 mPas and particularly from 1300 to 3000 mPas.

In the context of the present invention, “free-flowing” are also matrices, which are processable as a liquid, but later lose their liquid state, for example by curing or solidifying.

Curing of free-flowing matrices can result from various mechanisms, among which can be cited the most important hardening mechanisms of delayed water binding, cooling below the melting point, evaporation of solvents, crystallization, chemical reaction(s)—particularly polymerization—as well as changes in the rheological properties e.g. by modified shearing of the compound(s), as well as by radiation curing with UV, alpha, beta, or gamma radiation or microwaves.

Delayed water binding in the matrices can itself be realized in various ways. For example, there exist compounds, which are hydratable, anhydrous raw materials or raw materials in low hydration states, which can devolve into stable higher hydrates, and contain water. The formation of hydrates, which does not occur spontaneously, leads therefore to the binding of free water, which leads to a hardening of the compound.

Time-delayed water binding can also result for example, by incorporating hydrated salts into the matrices; on increasing the temperature, the salts dissolve in their own water of crystallization. On subsequently decreasing the temperature, the water of crystallization recombines, thus leading to a loss in the shapeability by simple means and to a solidification of the matrices.

The swelling of natural or synthetic polymers is also a time-delayed water-binding mechanism, which can be used according to the invention. Here, mixtures of unswollen polymer and suitable swelling agent, e.g. water, diols, glycerol etc., can be incorporated into the masses, with swelling and hardening taking place after dosing.

The most important mechanism of hardening by time-delayed water binding is the use of a combination of water and anhydrous or low-water raw materials, which slowly hydrate. Particularly appropriate substances for this purpose are those, which contribute to the washing performance in the washing or cleaning process. Preferred Ingredients of the matrices according to the invention are, for example, phosphates, carbonates, silicates and zeolites.

It is particularly preferred if the resulting hydrate forms have low melting points, since in this way a combination of the hardening mechanisms by internal drying and cooling is achieved. It is preferred where the matrices comprise 10 to 95% by weight, preferably 15 to 90% by weight, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances, which devolve, as a result of hydration, into a hydrate form having a melting point below 120° C., preferably below 100° C. and in particular below 80° C.

A further mechanism for hardening the matrices processed according to the invention is cooling during the processing of the matrices above their softening point. Processes in which the hardening of the shapeable matrices by cooling below the melting point are, accordingly, preferred.

Masses, which can be softened under the effect of temperature, can be formulated easily by mixing the desired further ingredients with a meltable or softenable substance, and heating the mixture to temperatures within the softening range of this substance and shaping the mixture at these temperatures. Particular preference is given here to using waxes, paraffins, polyalkylene glycols etc. as meltable or softenable substances. These are described below.

The meltable or softenable substances should have a melting range (solidification range) within a temperature range in which the other ingredients of the masses to be processed are not subjected to excessive thermal stress. In matrices preferred according to the invention, the meltable or softenable substances have a melting point above 30° C.

It has proven advantageous if the meltable or softenable substances do not exhibit a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range, which covers, under certain circumstances, several degrees Celsius. The meltable or softenable substances preferably have a melting range between about 45° C. and about 75° C. In the present case, this means that the melting range is within the given temperature interval, and does not define the width of the melting range. The breadth of the melting range is preferably at least 1° C., preferably about 2 to about 3° C.

The above-mentioned properties are usually satisfied by so-called waxes. “Waxes” are understood as meaning a series of natural or artificially obtained substances, which generally melt above 40° C. without decomposition, and are of relatively low-viscosity and are non-stringing at just a little above the melting point. They have a highly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups: natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, plant waxes, such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes, such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or uropygial grease, mineral waxes, such as ceresin or ozokerite (earth wax), or petrochemical waxes, such as petrolatum, paraffin waxes or microcrystalline waxes.

Chemically modified waxes include, for example, hard waxes, such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Meltable or softenable substances, which can be used for masses hardenable by cooling are also compounds from other classes of substances, which satisfy said requirements with regard to the softening point. Synthetic compounds which have proven suitable are, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG). Also suitable are synthetically prepared waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols with fatty acids from natural sources may also be used. This class of substance includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example, Shellack-KPS-Dreiring-SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.

Also covered by waxes for the purposes of the present invention are, for example, so-called wax alcohols. Wax alcohols are relatively high molecular weight, water-insoluble fatty alcohols having on average about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of relatively high molecular weight fatty acids (wax acids) as the major constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the solid particles coated in accordance with the invention can optionally also comprise wool wax alcohols, which is understood as meaning triterpenoid and steroid alcohols, for example lanolin, which is available, for example, under the trade name Argowax® (Pamentier & Co). As a constituent of the meltable or softenable substances, it is also possible to use, at least propartately, for the purposes of the present invention, fatty acid glycerol esters or fatty acid alkanolamides, but also, if desired, water-insoluble or only sparingly water-soluble polyalkylene glycol compounds.

Particularly preferred meltable or softenable substances in the masses to be processed are those from the group of polyethylene glycols (PEG) and/or polypropylene glycols (PPG), preference being given to polyethylene glycols having molecular weights between 1 500 and 36 000, particular preference being given to those having molecular weights from 2 000 to 6 000 and special preference being given to those having molecular weights from 3 000 to 5 000. Corresponding processes which are notable for the fact that the plastically shapeable mass(es) comprise(s) at least one substance from the group of polyethylene glycols (PEG) and/or polypropylene glycols (PPG) are also preferred. Here, particular preference is given to masses to be processed according to the invention that contain, as the sole meltable or softenable substances, propylene glycols (PPG) and/or polyethylene glycols (PEG). These substances have been described in detail above.

In a further preferred embodiment, the matrices to be processed according to the invention comprise paraffin wax as the major fraction. This means that at least 50% by weight of the total meltable or softenable substances present, preferably more, consist of paraffin wax. Particularly suitable paraffin wax contents (based on the total amount of meltable or softenable substances) are about 60% by weight, about 70% by weight or about 80% by weight, particular preference being given to even higher proparts of, for example, more than 90% by weight.

Compared with the other natural waxes mentioned, paraffin waxes have the advantage for the purposes of the present invention, that in an alkaline detergent product environment, no hydrolysis of the waxes takes place (as is to be expected, for example, in the case of wax esters), since paraffin wax does not contain hydrolysable groups.

Paraffin waxes consist primarily of alkanes and low fractions of iso- and cycloalkanes. Preferably, the paraffin to be used according to the invention has essentially no constituents with a melting point of more than 70° C., particularly preferably of more than 60° C. Below this melting temperature in the cleaning product liquor, fractions of high-melting alkanes in the paraffin may leave behind undesired wax residues on the surfaces to be cleaned or on the wares to be cleaned. Such wax residues generally lead to an unattractive appearance of the cleaned surface and should therefore be avoided.

Preferred matrices to be processed comprise, as meltable or softenable substances, at least one paraffin wax having a melting range from 50° C. to 60° C., preferred processes being those wherein the shapeable mass(es) comprise(s) a paraffin wax having a melting range of from 50° C. to 55° C.

Preferably, the content of alkanes, isoalkanes and cycloalkanes, which are solid at ambient temperature, (generally about 10 to about 30° C.) in the paraffin wax used is as high as possible. The larger the amount of solid wax constituents in a wax at room temperature, the more useful is the wax for the purposes of the present invention. As the propart of solid wax constituents increases, so does the resistance of the process end-products toward impact or friction with other surfaces, resulting in relatively long-lasting protection. High proparts of oils or liquid wax constituents can lead to a weakening of the shaped bodies or shaped body regions, as a result of which, pores are opened and the active substances are exposed to the ambient influences mentioned previously.

As well as comprising paraffin as the main constituent, the meltable or softenable substances may also comprise one or more of the abovementioned waxes or wax-like substances. In a further preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the mass and the shaped bodies or shaped body constituent formed therefrom are at least largely water-insoluble. At a temperature of about 30° C., the solubility in water should not exceed about 10 mg/l and should preferably be below 5 mg/l.

In such cases, however, the meltable or softenable substances should have the lowest possible solubility in water, even in water at elevated temperature, in order, as far as possible, to avoid temperature-dependent release of the active substances.

The principle described above is used for the delayed release of ingredients at a particular time point in the cleaning operation and can be used particularly advantageously if rinsing is carried out in the main rinse cycle at a relatively low temperature (for example 55° C.), so that the active substance is only released from the rinse aid particles in the rinse cycle at higher temperatures (approximately 70° C.).

Preferred masses to be processed according to the invention are those which comprise, as meltable or softenable substances, one or more substances having a melting range of from 40° C. to 75° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the weight of the mass.

A further mechanism, by which the hardening of the masses can take place, is the evaporation of solvents. For this, it is possible to prepare solutions or dispersions of the desired ingredients in one or more suitable, readily volatile solvents, which give off this/these solvent(s) after the shaping step and, in so doing, harden. Appropriate solvents are, for example, lower alkanols, aldehydes, ethers, esters etc, which are chosen depending on the further composition of the masses to be processed. Particularly suitable solvents for such processes in which the shapeable mass(es) harden(s) by evaporation of solvents are ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, and the acetic esters of the above alcohols, in particular ethyl acetate.

The evaporation of the abovementioned solvents may be accelerated by heating after shaping, or by air movement. Combinations of the measures specified are also suitable for this purpose, for example, the blowing of the cut-to-length shaped bodies with warm or hot air.

A further mechanism, which may form the basis for hardening, is that of crystallization.

Crystallization, as a mechanism on which the hardening is based, may be utilized by using, for example, melts of crystalline substances as the basis of one or more shapeable matrices. Following processing, systems of this kind undergo transition to a higher state of order, which in turn leads to hardening of the overall formed, shaped body. Alternatively, crystallization may take place by crystallization from supersaturated solution. In the context of the present invention, supersaturation refers to a metastable state in which, in a closed system, more of one substance is present than is required for saturation. A supersaturated solution obtained, for example, by supercooling accordingly comprises more dissolved substance than it should contain in thermal equilibrium. The excess of dissolved substance may be brought to instantaneous crystallization by seeding with seed crystals or dust particles or by agitating the system. In the context of the present invention, the term “supersaturated” always refers to a temperature of 20° C. If x grams of a substance per liter dissolve in a defined solvent at a temperature of 20° C., then the solution, in the context of the present invention, may be referred to as “supersaturated” if it contains (x+y) grams of the substance per liter, y being>0. Consequently, in the context of the present invention, solutions referred to as “supersaturated” include those which at an elevated temperature are used as the basis of a mass to be processed and are processed at this temperature, in which more dissolved substance is present in the solution than would dissolve in the same amount of solvent at 20° C.

The term “solubility” is understood by the present invention as meaning the maximum amount of a substance, which the solvent is able to accommodate at a certain temperature, i.e., the fraction of the dissolved substance in a solution saturated at the temperature in question. Where a solution contains more dissolved substance than it should contain in thermodynamic equilibrium at a given temperature (for example, in the case of supercooling), it is referred to as supersaturated. By seeding with seed crystals, it is possible to cause the excess to precipitate as a sediment in the solution, which is now just saturated. A solution saturated in respect of a substance may, however, also dissolve other substances (for example, it is still possible to dissolve sugar in a saturated solution of common salt).

The state of supersaturation can be achieved, as described above, by slow cooling or by supercooling a solution, provided the dissolved substance is more soluble in the solvent at higher temperatures. Other ways of obtaining supersaturated solutions are, for example, the combination of two solutions whose ingredients react to form another substance, which does not immediately precipitate out (hindered or retarded precipitation reactions). The latter mechanism is particularly suitable as a basis for the formation of matrices for processing in accordance with the invention.

In principle, the state of supersaturation is achievable in any kind of solution, although the use of the principle described in the present specification finds its application, as already mentioned, in the production of detergents. Accordingly, some systems, which in principle tend to form supersaturated solutions, are less suitable for use in accordance with the invention, since the substance systems on which they are based cannot be used, on ecological, toxicological, or economic grounds. In addition to nonionic surfactants or common non-aqueous solvents, therefore, particular preference is given to processes according to the invention with the last-mentioned hardening mechanism wherein a supersaturated aqueous solution is used as the basis of at least one matrix to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention refers to the saturated solution at 20° C. By using solutions at a temperature above 20° C., it is easy to attain the state of supersaturation. Processes according to the invention wherein the crystallization-hardening mass during processing has a temperature of between 35 and 120° C., preferably between 40 and 110° C., particularly preferably between 45 and 90° C., and in particular between 50 and 80° C., are preferred in the context of the present invention.

Since the detergent shaped bodies produced are generally neither stored at elevated temperatures nor later used at these elevated temperatures, the cooling of the mixture leads to the precipitation from the supersaturated solution of the fraction of dissolved substance which was present in the solution above the saturation limit at 20° C. Thus, on cooling, the supersaturated solution may be divided into a saturated solution and a sediment. It is, however, also possible that, owing to recrystallization and hydration phenomena, the supersaturated solution solidifies on cooling to form a solid. This is the case, for example, if certain salts containing water of hydration dissolve in their water of crystallization on heating. In this case, supersaturated solutions are often formed on cooling which, by mechanical action or addition of seed crystal solidify to a solid—the salt, containing water of crystallization, as the state which is thermodynamically stable at room temperature. This phenomenon is known, for example, for sodium thiosulfate pentahydrate and sodium acetate trihydrate, the latter salt in particular, containing water of hydration, being advantageously useful in the form of the supersaturated solution in the process according to the invention. Specific detergent ingredients as well, such as phosphonates, for example, display this phenomenon and are outstandingly suitable in the form of the solutions as granulation auxiliaries. For this purpose the corresponding phosphonic acids (see below) are neutralized with concentrated alkali metal hydroxide solutions, the solution being heated by the heat of neutralization. On cooling, these solutions form solids of the corresponding alkali metal phosphonates. By incorporating further detergent ingredients into the solutions while still warm, it is possible in accordance with the invention to prepare processable matrices of different composition. Particularly preferred processes according to the invention are those wherein the supersaturated solution used as a basis of the hardening matrix solidifies at room temperature to form a solid. It is preferred in this case that the formerly supersaturated solution, following solidification to form a solid, cannot be converted back into a supersaturated solution by heating to the temperature at which the supersaturated solution was formed. This is the case, for example, with the phosphonates mentioned.

As mentioned above, the supersaturated solution used as a basis of the hardening matrix may be obtained in a number of ways and then processed following optional admixing of further ingredients. One simple way, for example, is to prepare the supersaturated solution, which is used as a basis for the hardening matrix, by dissolving the dissolved substance in heated solvent. If the amounts of the dissolved substance dissolved in this way in the heated solvent are higher than those which would have dissolved at 20° C., then a solution is present that is supersaturated in the sense of the present invention, and which, either hot (see above), or after cooling and in the metastable state, could be introduced into the mixer.

It is also possible to remove the water from salts containing water of hydration by “dry” heating and to dissolve them in their own water of crystallization (see above). This too, is a method of preparing super-saturated solutions that may be used in the context of the present invention.

Another way is to add a gas or other fluid or solution to a non-supersaturated solution, such that the dissolved substance reacts in the solution to form a less soluble substance or dissolves to a lesser extent in the mixture of the solvents. The combination of two solutions each containing two substances, which react with one another to form a less soluble substance, is likewise a method of preparing supersaturated solutions, provided the less-soluble substance does not precipitate out instantaneously. Processes which are likewise preferred in the context of the present invention are those wherein the supersaturated solution used as the basis of the hardening matrix is prepared by combining two or more solutions. Examples of such methods for preparing supersaturated solutions are dealt with below.

It is preferred when the supersaturated aqueous solution is obtained by combining an aqueous solution of one or more acidic ingredients of detergents, preferably from the group of the surfactant acids, the builder acids and the complexing agent acids, and an aqueous alkali solution, preferably an aqueous alkali metal hydroxide solution, in particular an aqueous sodium hydroxide solution.

Among the representatives of said classes of compound that have already been mentioned above, the phosphonates in particular occupy an outstanding position in the context of the present invention. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is obtained by combining an aqueous phosphonic acid solution in concentrations above 45% by weight, preferably above 50% by weight, and in particular above 55% by weight, based in each case on the phosphonic acid solution, and an aqueous sodium hydroxide solution in concentrations above 35% by weight, preferably above 40% by weight, and in particular above 45% by weight, based in each case on the sodium hydroxide solution.

In accordance with the invention, the hardening of the matrix may also occur by means of chemical reaction(s), in particular polymerization. In principle in this context, all chemical reactions are suitable which, starting from one or more liquid to paste-like substances, produce solids, by reaction with (an) other substance(s). In this context, chemical reactions, which do not lead suddenly to said change of state, are especially suitable. From the multitude of chemical reactions that lead to solidification phenomena, suitable reactions are particularly those in which larger molecules are built up from smaller molecules. These reactions preferably include, in turn, reactions in which many small molecules react to form (one) larger molecule(s). These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the finished, cut-to-length, shaped body its strength.

In view of the intended use of the products prepared in accordance with the invention, a hardening mechanism is preferred for forming those solid substances from liquid or paste-like starting materials, which in any case are to be used as ingredients in the detergent, for example cobuilders, soil repellents, and soil release polymers. Such cobuilders may originate, for example, from the groups of the polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins etc. These classes of substance are described below.

A further mechanism by which the shapeable mass(es) may harden in the context of the present invention is that of hardening as a result of a change in rheological properties.

In this case, use is made of the fact that the rheological properties of certain substances drastically change in part as a function of shear forces. Examples of such systems, which are familiar to the person skilled in the art, are phyllosilicates, for example, which under shearing have a highly thickening action in appropriate matrices and can lead to masses of firm consistency.

In summary, based on industrial feasibility, particularly preferred portion packaging are characterized in that the free-flowing material is a solidified melt.

As well as being a (optionally solidifiable or hardenable) liquid, the free-flowing material can also be particulate. Preferred portion packaging according to the invention are characterized in that the free-flowing material is a totality of particles, whose mean particle size lies below 1200 μm, preferably below 300 μm, particularly preferably below 250 μm and particularly below 200 μm.

Depending on the desired application, the portions according to the invention can comprise various detergent ingredients. In consequence, the various regions, such as the core, individual core regions (in multi-phase cores), matrix or individual matrix regions can be used to separate incompatible ingredients.

The most important ingredients that can be comprised in the inventive portions are described below.

Detergent portions according to the invention preferably comprise one or more surfactant(s), anionic, nonionic, cationic and/or amphoteric surfactants being able to be used. For textile detergents and from a performance viewpoint, preference is given to mixtures of anionic and nonionic surfactants, wherein the proportion of anionic surfactant should be higher than the proportion of nonionic surfactant. The total surfactant content of the detergent portions is preferably below 30% by weight, based on the total composition. Nonionic surfactants were already described above as optional plasticizers for the envelope. The same substances can also be used in the portions as detersive substances and reference can be made to the previous explanations.

Furthermore, as further nonionic surfactants, use may also be made of alkyl glycosides of the general formula RO(G)_(x), where R is a primary straight-chain or methyl-branched aliphatic radical, especially an aliphatic radical methyl-branched in position 2, containing 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization, x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10; preferably, x is from 1.2 to 1.4.

A further class of preferred nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type, may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula VIII,

where RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R¹ is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and from 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances, which are customarily obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the following formula IX,

where R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R¹ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R² is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C₁₋₄ alkyl radicals or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of said radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, e.g. glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted to the desired polyhydroxy fatty acid amides, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The preferred content of nonionic surfactants in the inventive detergent portions that are suitable for washing textiles ranges from 5 to 20 wt. %, preferably 7 to 15 wt. % and especially 9 to 14 wt. %, each based on the total composition.

Low-foaming nonionic surfactants are preferably used in automatic dishwasher compositions.

In combination with the cited surfactants, anionic, cationic and/or amphoteric surfactants can also be added. Due to their foaming behavior, they are only of limited importance in automatic dishwasher formulations, and are mostly added in amounts of less than 10 wt. %, mostly even less than 5 wt. %, for example from 0.01 to 2.5 wt. %, each based on the composition. On the other hand, these surfactants have a markedly higher importance in detergents. Consequently, the detergent portions according to the invention may also comprise anionic, cationic and amphoteric surfactants as surfactant components.

The products according to the invention may, for example, comprise cationic compounds of the formulae X, XI or XII as cationic active substances:

in which each group R¹, independently of one another, is chosen from C₁₋₆-alkyl, -alkenyl or -hydroxyalkyl groups; each group R², independently of one another, is chosen from C₈₋₂₈-alkyl or -alkenyl groups; R³═R¹ or (CH₂)_(n)-T-R²; R⁴═R¹ or R² or (CH₂)_(n)-T-R²; T=-CH₂—, —O—CO— or —CO—O— and n is an integer from 0 to 5.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C₉₋₁₃ alkylbenzene sulfonates, olefin sulfonates, i.e., mixtures of alkene sulfonates and hydroxyalkane sulfonates, and also disulfonates, as are obtained, for example, from C₁₂₋₁₈ monoolefins having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates are also suitable, which are obtained from C₁₂₋₁₈ alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, respectively. Likewise suitable, in addition, are the esters of α-sulfo fatty acids (ester sulfonates), e.g., the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to mean the monoesters, diesters and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, examples being those of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

Preferred alk(en)yl sulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of C₁₂-C₁₈ fatty alcohols, examples being those of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C₁₀-C₂₀ oxo alcohols, and those monoesters of secondary alcohols of these chain lengths. Preference is also given to alk(en)yl sulfates of said chain lengths, which contain a synthetic straight-chain alkyl radical, prepared on a petrochemical basis, and which have degradation behavior similar to that of the corresponding compounds based on fatty-chemical raw materials. From a laundry detergents viewpoint, the C₁₂-C₁₆ alkyl sulfates and C₁₂-C₁₅ alkyl sulfates, and also C₁₄-C₁₅ alkyl sulfates, are preferred. In addition, 2,3-alkyl sulfates, which may for example be prepared in accordance with U.S. Pat. Nos. 3,234,258 or 5,075,041 and obtained as commercial products from Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric monoesters of the straight-chain or branched C₇₋₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C₉₋₁₁ alcohols containing on average 3.5 mol of ethyene oxide (EO) or C₁₂₋₁₈ fatty alcohols containing from 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning products only in relatively small amounts, for example, in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C₈₋₁₈ fatty alcohol radicals or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols which themselves represent nonionic surfactants (for description, see below). Particular preference is given in turn to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrowed homolog distribution. Similarly, it is also possible to use alk(en)ylsuccinic acid containing preferably 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

Further suitable anionic surfactants are, in particular, soaps. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, mixtures of soaps derived from natural fatty acids, e.g., coconut, palm kernel, or tallow fatty acids.

The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The amount of anionic surfactants in preferred textile detergents according to the invention ranges from 5 to 25 wt. %, preferably 7 to 22 wt. % and especially 10 to 20 wt. %, each based on the total composition. Inventive detergents for automatic dishwashers are preferably free of anionic surfactants.

In the context of the present invention, preferred compositions additionally comprise one or more materials from the group consisting of builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescents, colorants, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, feeding promoters, anti-crease agents, color-transfer inhibitors, antimicrobials, germicides, fungicides, antioxidants, corrosion inhibitors, antistats, ironing auxiliaries, hydrophobes and impregnation agents, swelling agents and anti-slip agents as well as UV absorbers.

The inventive compositions may comprise builders—specially among which are phosphates, silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids as well as mixtures thereof.

According to the invention, the generally known phosphates may be used as builders, providing their use should not be avoided on ecological grounds. Among the large number of commercially available phosphates, alkali metal phosphates have the greatest importance in the detergent industry, pentasodium triphosphate and pentapotassium triphosphate (sodium and potassium tripolyphosphate) being particularly preferred.

“Alkali metal phosphates” is the collective term for the alkali metal (more particularly sodium and potassium) salts of the various phosphoric acids, including metaphosphoric acids (HPO₃)_(n) and orthophosphoric acid (H₃PO₄) and representatives of higher molecular weight. The phosphates combine several advantages: they act as alkalinity sources, prevent lime deposits on machine parts and lime incrustations in fabrics and, in addition, contribute towards the cleaning effect.

Sodium dihydrogen phosphate NaH₂PO₄ exists as the dihydrate (density 1.91 gcm⁻³, melting point 60° C.) and as the monohydrate (density 2.04 gcm⁻³). Both salts are white, readily water-soluble powders that on heating, lose the water of crystallization and at 200° C. are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na₂H2P₂O₇) and, at higher temperatures into sodium trimetaphosphate (Na₃P3O₉) and Maddrell's salt (see below). NaH₂PO₄ shows an acidic reaction. It is formed by adjusting phosphoric acid with sodium hydroxide to a pH value of 4.5 and spraying the resulting “mash”. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH₂PO₄, is a white salt with a density of 2.33 g^(m−3), has a melting point of 253° C. [decomposition with formation of potassium polyphosphate (KPO₃)_(x)] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na₂HPO₄, is a colorless, readily water-soluble crystalline salt. It exists in anhydrous form and with 2 mol (density 2.066 gcm⁻³, water loss at 95° C.), 7 mol (density 1.68 gcm⁻³, melting point 48° C. with loss of 5H₂O) and 12 mol of water (density 1.52 gcm⁻³, melting point 35° C. with loss of 5H₂O), becomes anhydrous at 100° C. and, on fairly intensive heating, is converted into the diphosphate Na₄P₂O₇. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K₂HPO₄, is an amorphous white salt, which is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na₃PO₄, consists of colorless crystals with a density of 1.62 gcm⁻³ and a melting point of 73-76° C. (decomposition) as the dodecahydrate, a melting point of 100° C. as the decahydrate (corresponding to 19-20% P₂O₅) and a density of 2.536 gcm⁻³ in anhydrous form (corresponding to 39-40% P₂O₅). Trisodium phosphate is readily soluble in water through an alkaline reaction and is prepared by concentrating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH by evaporation. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K₃PO₄, is a white deliquescent granular powder with a density of 2.56 gcm⁻³, has a melting point of 1340° C. and is readily soluble in water through an alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulfate. Despite their higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na₄P₂O₇, exists in anhydrous form (density 2.534 gcm⁻³, melting point 988° C., a figure of 880° C. has also been mentioned) and as the decahydrate (density 1.815-1.836 gcm⁻³, melting point 94° C. with loss of water). Both substances are colorless crystals, which dissolve in water through an alkaline reaction. Na₄P₂O₇ is formed when disodium phosphate is heated to more than 200° C. or by reacting phosphoric acid with soda in a stoichiometric ratio and spray drying the solution. The decahydrate complexes heavy metal salts and hardness salts and, hence, reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), K₄P₂O₇, exists in the form of the trihydrate and is a colorless hygroscopic powder with a density of 2.33 gcm⁻³, is soluble in water, the pH of a 1% solution at 25° C. being 10.4.

Relatively high molecular weight sodium and potassium phosphates are formed by condensation of NaH₂PO₄ or KH₂PO₄. They may be divided into cyclic types, namely the sodium and potassium metaphosphates, and chain types, the sodium and potassium polyphosphates. The chain types in particular are known by various different names: fused or calcined phosphates, Graham's salt, Kurrol's salt and Maddrell's salt. All higher sodium and potassium phosphates are known collectively as condensed phosphates.

The industrially important pentasodium triphosphate, Na₅P₃O₁₀ (sodium tripolyphosphate), is anhydrous or crystallizes with 6H₂O to a non-hygroscopic, white, water-soluble salt, which has the general formula NaO—[P(O)(ONa)—O]_(n)—Na where n=3. Around 17 g of the salt, free from water of crystallization dissolve in 100 g of water at room temperature, around 20 g at 60° C. and around 32 g at 100° C. After heating the solution for 2 hours to 100° C., around 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide in a stoichiometric ratio and the solution is spray dried. Similarly to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K₅P₃O₁₀ (potassium tripolyphosphate), is marketed for example in the form of a 50% by weight solution (>23% P₂O5, 25% K₂O). The potassium polyphosphates are widely used in the detergent industry. Sodium potassium tripolyphosphates, which may also be used in accordance with the present invention, also exist. They are formed for example when sodium trimetaphosphate is hydrolyzed with KOH: (NaPO₃)₃+2KOH→Na₃K₂P₃O₁₀+H₂O

According to the invention, they may be used in exactly the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures thereof. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate may also be used in accordance with the invention.

Suitable crystalline, layered sodium silicates correspond to the general formula NaMSi_(x)O2_(x+1).H₂O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x being 2, 3 or 4. Preferred crystalline, layered silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both β- and δ-sodium disilicates Na₂Si₂O₅.yH₂O are particularly preferred.

Other useful builders are amorphous sodium silicates with a modulus (Na₂O:SiO₂ ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6, which dissolve with a delay and exhibit multiple wash cycle properties. The delay in dissolution compared with conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compressing/compacting or by over drying. In the context of the invention, the term “amorphous” is also understood to encompass “X-ray amorphous”. In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce indistinct or even sharp diffraction maxima in electron diffraction experiments. This can be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and especially up to at most 20 nm being preferred. Especially preferred are densified/compacted amorphous silicates, compounded amorphous silicates and over dried X-ray amorphous silicates.

Preferably, zeolite A and/or zeolite P are used as the fine crystalline, synthetic zeolite that contains bound water. Zeolite MAP® (commercial product of Crosfield Ltd) is a particularly preferred zeolite P. However, zeolite X as well as mixtures of A, X and/or P are also suitable. A commercially available and preferred for use zeolite, in the context of the present invention is, for example, also a cocrystallizate of zeolite X and zeolite A (approximately 80% by weight zeolite X), which is sold by CONDEA Augusta S.p.A. under the trade name VEGOBOND AX® and may be described by the formula: nNa₂O.(1-n)K₂O.Al₂O₃.(2-2.5)SiO₂.(3.5-5.5)H₂O

The zeolite can be used as a spray-dried powder or also as an undried, still moist from its manufacture, stabilized suspension. When the zeolite is used in the form of a suspension, then small quantities of nonionic surfactants can be comprised therein as stabilizers, for example 1 to 3 wt. %, based on the zeolite, of ethoxylated C₁₂-C₁₈ fatty alcohols with 2 to 5 ethylene oxide groups, C₁₂-C₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably comprise 18 to 22 wt. %, particularly 20 to 22 wt. % of bound water.

Additional, important builders are especially the carbonates, citrates and silicates. Preferably, trisodium citrate and/or pentasodium tripolyphosphate and/or sodium carbonate and/or sodium bicarbonate and/or gluconates and/or silicate builders from the class of disilicates and/or metasilicates are used.

Additional components can be alkaline entities. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the cited materials can be used as alkaline entities, where in the context of this invention, the alkali carbonates are preferably used, especially sodium carbonate or sodium sesquicarbonate.

A particularly preferred builder system comprises a mixture of tripolyphosphate and sodium carbonate.

Another particularly preferred builder system comprises a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

Additional constituents can be present as well, detergents or rinsing agents according to the invention being preferred that further comprise one or more substances from the group of acidifiers, chelating agents or deposit-inhibiting polymers.

Both mineral acids and organic acids are available as acidifiers, in so far as they are compatible with the customary constituents. The solid mono-, oligo- and polycarboxylic acids are used, particularly for reasons of consumer protection and safety of handling. Preferred among this group, in turn, are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids, such as amidosulfonic acid, may likewise be used. The anhydrides of these acids can also be used as acidifiers, maleic anhydride and succinic anhydride especially being commercially available. A product, which is commercially available and which can likewise be preferably used as an acidifier in the context of the present invention, is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Chelating agents represent a further possible group of constituents. Chelating agents are substances that form cyclic compounds with metal ions, wherein a single ligand occupies more than one coordination position on a central atom, i.e. is at least “bidentate”. In this case, normally linear compounds are ring closed by complex formation with an ion. The number of bound ligands depends on the coordination number of the central ion.

Useable and preferred chelating agents, in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is, polymers that have functional groups, either in the main chain itself or in side chains, which can act as ligands and normally react with suitable metal atoms to form chelate complexes, are useable according to the invention. Here, the polymer bound ligands of the resulting metal complexes can stem from only one macromolecule or rather belong to different polymer chains. The latter leads to crosslinked materials, in so far that the complex-forming polymers were not already crosslinked through covalent bonds.

Complexing groups (ligands) of typical complex-forming polymers are iminodiacetic acid-, hydroxyquinoline-, thiourea-, guanidine-, dithiocarbonate-, hydroxamic acid-, amidoxime-, aminophosphoric acid-, (cycl.) polyamino-, mercapto-, 1,3-dicarbonyl- and crown ether radicals with—in some cases—very specific activities towards ions of different metals. The base polymers of many, also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starches or chitin are also complex-forming polymers. Moreover, these can be given additional functionalities by polymer-analogous conversions.

In the context of the present invention, detergent portions are particularly preferred, which comprise one or more chelating agents from the groups of

-   -   i) Polycarboxylic acids, in which the sum of the carboxyl and         hydroxyl groups, when present, is at least 5,     -   ii) Nitrogen-containing mono- or polycarboxylic acids,     -   iii) Geminal diphosphonic acids,     -   iv) Aminophosphonic acids     -   v) Phosphonopolycarboxylic acids     -   vi) Cyclodextrins         in quantities greater than 0.1 wt. %, preferably greater than         0.5 et. %, particularly preferably greater than 1 wt. % and         especially greater than 2.5 wt. %, each based on the weight of         the composition.

In the context of the present invention, all complexing agents of the prior art can be used. They can belong to various chemical groups. Preferably, the following are used alone or together in a mixture:

-   -   a) Polycarboxylic acids, in which the sum of the carboxyl and         hydroxyl groups, when present, is at least 5, like gluconic         acid,     -   b) Nitrogen-containing mono- or polycarboxylic acids like         ethylenediaminetetraacetic acid (EDTA),         N-hydroxyethylethylenediaminetriacetic acid,         diethylenetriaminopentaacetic acid, hydroxyethyliminodiacetic         acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic         acid, N, N-di-(β-hydroxyethyl)glycine,         N-(1,2-dicarboxy-2-hydroxyethyl)glycine,         N-(1,2-dicarboxy-2-hydroxyethyl)aspartic acid, or         nitrilotriacetic acid (NTA),     -   c) Geminal diphosphonic acids like         1-hydroxyethane-1,1-diphosphonic acid (HEDP), its higher         homologs with up to 8 carbon atoms as well as hydroxy-or         aminogroup-containing derivatives thereof and         1-aminoethane-1,1-diphosphonic acid, its higher homologs with up         to 8 carbon. atoms as well as hydroxy- or amino group-containing         derivatives thereof,     -   d) Aminophosphonic acids like ethylenediaminetetra         (methylenephosphonic acid),         diethylenetriaminepenta(methylenephosphonic acid) or nitrilotri         (methylenephosphonic acid),     -   e) Phosphonopolycarboxylic acids like         2-phosphonobutane-1,2,4-tricarboxylic acid as well as     -   f) Cyclodextrins.

In the context of this patent application, the polycarboxylic acids a) are understood to be carboxylic acids—also monocarboxylic acids, in which the sum of the carboxyl- and the hydroxyl groups amount to at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, particularly EDTA, are preferred. At the required alkaline pH of the treatment solutions according to the invention, the complexing agents are present, at least partially, as anions. It is not important whether they are brought in as acids or as salts. When they are added as salts, alkali-, ammonium- or alkylammonium salts are preferred.

Deposit-inhibiting polymers can also be comprised in the inventive compositions. These substances, which may be chemically different, stem, for example from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20 000 daltons, polymers with molecular weights of less than 15 000 daltons being preferred.

Deposit-inhibiting polymers can also exhibit co-builder properties. Polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic co-builders (see below) as well as phosphonates etc. can be added as co-builders in the inventive automatic dishwasher rinse agents. These classes of substance are described below.

Organic builder substances which may be used are, for example, the polycarboxylic acids in the form of their sodium salts, the term polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable on ecological grounds, and also mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.

The acids per se may also be used. In addition to their builder effect, the acids typically also possess the property of an acidifying component and therefore serve to establish a lower and milder pH for detergents. In this context, particular mention may be made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any desired mixtures thereof.

Polymeric polycarboxylates are also suitable builders or deposit-inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, examples being those having a relative molecular weight of from 500 to 70 000 g/mol.

For the purposes of this document, the molecular weights reported for polymeric polycarboxylates are weight-average molecular weights, M_(w), of the respective acid form, determined fundamentally by means of gel permeation chromatography (GPC) using a UV detector. The measurement was made against an external polyacrylic acid standard, which owing to its structural similarity to the polymers under investigation, provides realistic molecular weight values. These figures differ markedly from the molecular weight values obtained using polystyrenesulfonic acids as the standard. The molecular weights measured against polystyrenesulfonic acids are generally much higher than the molecular weights reported in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight from 500 to 20 000 g/mol. Owing to their superior solubility, preference in this group may again be given to the short-chain polyacrylates, which have molecular weights from 1000 to 10 000 g/mol, and with particular preference from 1000 to 4000 g/mol.

Both polyacrylates and copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers as well as, when required, additional ionic or nonionic monomers are used in particularly preferred compositions according to the invention. The sulfonic acid-containing copolymers are described in more detail below.

Copolymeric polycarboxylates are also suitable, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers, which have been found particularly suitable, are those of acrylic acid with maleic acid, which contain from 50 to 90% by weight acrylic acid and from 50 to 10% by weight maleic acid. Their relative molecular weight, based on free acids, is generally from 2000 to 70 000 g/mol, preferably from 20 000 to 50 000 g/mol, and in particular from 30 000 to 40 000 g/mol.

The (co)polymeric polycarboxylates can be used either as powders or as aqueous solutions. The (co)polymeric polycarboxylate content of the compositions is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.

Particular preference is also given to biodegradable polymers comprising more than two different monomer units, examples being those comprising, as monomers, salts of acrylic acid and of maleic acid, and also vinyl alcohol or vinyl alcohol derivatives, or those comprising, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and also sugar derivatives. Further preferred copolymers are those, whose monomers are preferably acrolein and acrylic acid/acrylic acid salts, respectively acrolein and vinyl acetate.

Similarly, further preferred builder substances that may be mentioned include polymeric aminodicarboxylic acids, their salts or their precursor substances. Particular preference is given to polyaspartic acids and their salts and derivatives, which have not only cobuilder properties but also a bleach-stabilizing action.

Further suitable builder substances are polyacetals, which may be obtained by reacting dialdehydes with polyol carboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.

Further suitable organic builder substances are dextrins, examples being oligomers and polymers of carbohydrates, which may be obtained by partial hydrolysis of starches. The hydrolysis can be conducted by customary processes; for example, acid-catalyzed or enzyme-catalyzed processes. The hydrolysis products preferably have average molecular weights in the range from 400 to 500 000 g/mol. Preference is given here to a polysaccharide having a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide in comparison to dextrose, which possesses a DE of 100. It is possible to use both maltodextrins having a DE of between 3 and 20 and dried glucose syrups having a DE of between 20 and 37, and also so-called yellow dextrins and white dextrins having higher molecular weights in the range from 2000 to 30 000 g/mol.

The oxidized derivatives of such dextrins comprise their products of reaction with oxidizing agents, which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Likewise suitable is an oxidized oligosaccharide. A product oxidized at C₆ of the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine N,N′-disuccinate (EDDS) is used preferably in the form of its sodium or magnesium salts. Further preference in this context is given to both glycerol disuccinates and glycerol trisuccinates. Suitable dosages in formulations containing zeolite and/or silicate are from 3 to 15% by weight.

Examples of further useful organic cobuilders are acetylated hydroxycarboxylic acids and their salts, which may also be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxyl group, and not more than two acid groups.

A further class of substance having cobuilder properties is represented by the phosphonates. The phosphonates in question are, in particular, hydroxyalkane- and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is used preferably as the sodium salt, the disodium salt being neutral and the tetrasodium salt giving an alkaline (pH 9) reaction. Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologs. They are used preferably in the form of the neutrally reacting sodium salts, e.g., as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. As a builder in this case, preference is given to using HEDP from the class of the phosphonates. Furthermore, the aminoalkanephosphonates possess a pronounced heavy metal binding capacity. Accordingly, and especially if the compositions also contain bleach, it may be preferred to use aminoalkanephosphonates, especially DTPMP, or to use mixtures of said phosphonates.

In addition to the substances from the cited substance classes, the inventive compositions can comprise further customary detergent ingredients, bleaches, bleach activators, enzymes, silver protectants, colorants and fragrances being of particular importance. These substances are described below.

Among the compounds used as bleaches, which yield H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaches are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrate as well as H₂O₂-generating peracid salts or peracids, such as peroxyphthalates, diperazelaic acid, phthaloimino peracid or diperdodecanoic diacid.

Bleach activators can be incorporated into detergents in order to achieve an improved bleaching activity when washing at temperatures of 60° C. or below. Bleach activators which may be used are compounds which under perhydrolysis conditions give rise to aliphatic peroxy carboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted or unsubstituted perbenzoic acid. Suitable substances are those, which carry O-acyl and/or N-acyl groups of the stated number of carbon atoms, and/or substituted or unsubstituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators, or instead of them, it is also possible to incorporate what are known as bleaching catalysts into the tablets. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Other bleaching catalysts which can be used include Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands, and also Co-, Fe-, Cu- and Ru-ammine complexes.

Suitable enzymes include in particular those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, and mixtures of said enzymes. In the laundry, all of these hydrolases contribute to removing stains, such as proteinaceous, fatty or starchy marks and graying. Cellulases and other glycosyl hydrolases may also contribute by removing pilling and microfibrils, to the retention of color and to an increase in the softness of the textile. For bleaching and/or for inhibiting color transfer it is also possible to use oxidoreductases. Especially suitable enzymatic active substances are those obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens, and also from genetically modified variants thereof. Preference is given to the use of proteases of the subtilisin type, and especially to proteases obtained from Bacillus lentus. Of particular interest in this context are enzyme mixtures, examples being those of protease and amylase or protease and lipase or lipolytic enzymes, or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes, or protease, lipase or lipolytic enzymes and cellulase, but especially protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven suitable in some cases. The suitable amylases include, in particular, α-amylases, iso-amylases, pullulanases, and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, and mixtures thereof. Because different types of cellulase differ in their CMCase and Avicelase activities, specific mixtures of the cellulases may be used to establish the desired activities.

The enzymes may be adsorbed on carrier substances or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules may be, for example, from about 0.1 to 5% by weight, preferably from 0.12 to about 2% by weight.

According to the invention, detergent portions for automatic dishwashers can contain corrosion inhibitors to protect the wares or the machine, silver protectants especially being of particular importance in automatic dishwashers. The known substances of the prior art may be used. In general it is possible to use, in particular, silver protectants selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and transition metal salts or transition metal complexes. Particular preference is given to the use of benzotriazole and/or alkylaminotriazole. Frequently encountered in cleaning formulations, furthermore, are agents containing active chlorine, which may significantly reduce corrosion of the silver surface. In chlorine-free cleaning products, particular use is made of oxygen-containing and nitrogen-containing organic redox-active compounds, such as difunctional and trifunctional phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these classes of compound. Inorganic compounds in the form of salts and complexes, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, also find frequent application. Preference is given in this context to the transition metal salts selected from the group consisting of manganese and/or cobalt salts and/or complexes, particularly preferably cobalt ammine complexes, cobalt acetato complexes, cobalt carbonyl complexes, the chlorides of cobalt or of manganese and manganese sulfate. Similarly, zinc compounds may be used to prevent corrosion of the wares.

A wide number of the most diverse salts can be incorporated from the group of inorganic salts as electrolytes. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From the industrial manufacturing stand point, the addition of NaCl or MgCl₂ to the inventive compositions is preferred. The amount of electrolytes in the inventive compositions normally ranges from 0.5 to 5 wt. %.

In order to adjust the pH of the inventive composition to the desired range, the addition of pH-modifiers may be indicated. All known acids or bases can be added, in so far as their addition is not forbidden on technical or ecological grounds or grounds of consumer protection. Typically, the amount of these modifiers is not more than 5 wt. % of the total formulation.

In order to enhance the esthetic impression of the detergent composition of the invention, they may be colored with appropriate dyes. Preferred dyes, whose selection presents no difficulty whatsoever to the skilled worker, have a high level of storage stability and insensitivity toward the other ingredients of the composition and towards light, and have no pronounced substantivity toward textile fibers, so as not to stain them.

Foam inhibitors, which may be used in the compositions in accordance with the invention, are suitably, for example, soaps, paraffins or silicone oils, which may if desired have been deposited on carrier materials. Suitable anti-redeposition agents (also called soil-repellents), formulated according to the invention as textile detergents, are, for example, nonionic cellulose ethers like methyl cellulose and methyl hydroxypropyl cellulose with a content of from 15 to 30% by weight of methoxy groups and a hydroxypropyl group content of from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as polymers known from the prior art, of phthalic acid and/or terephthalic acid, and/or derivatives thereof, especially polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, particular preference is given to the sulfonated derivatives of phthalic acid polymers and of terephthalic acid polymers.

In order to eliminate graying or yellowing of treated textiles, optical brighteners (known as “whiteners”) can be added to the inventive compositions, formulated according to the invention as textile detergents. These substances attach onto the fibers and cause a brightening and a simulated bleach effect, in that they convert part of the invisible UV radiation of sunlight into longer wavelength light, the absorbed ultraviolet light from the sunlight being emitted as weakly blue fluorescence with the result that the yellow tinge of the gray or yellowed washing becomes pure white. Suitable compounds are based on for example, the classes of substances 4,4′-diamino-2,2′-stilbene disulfonic acids (flavonic acids), 4,4′-distyrylbiphenylene, methyl umbelliferones, coumarins, dihydroquinolines, 1,3-diarylpyrazolines, naphthoic acid imides, benzoxazole-, benzisoxazole- and benzimidazole systems, as well as pyrene derivatives substituted with heterocycles. The optical brighteners are normally added in quantities between 0.05 and 0.3 wt. %, based on the finished composition.

Graying inhibitors have the function of keeping the dirt detached from the fiber in suspension in the liquor, thus preventing the redeposition of the dirt. Suitable for this purpose are water-soluble colloids, usually organic in nature, examples being glue, gelatin, salts of ethersulfonic acids of starch or of cellulose, or salts of acidic sulfuric acid esters of cellulose or of starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. In addition, soluble starch preparations and starch products other than those mentioned above may be used, examples being degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone may also be used. Preference, however, is given to the use of cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions.

The inventive compositions can also be provided with additional advantages. For example, compositions formulated according to the invention as textile detergents are formulated for inhibiting color transfers, compositions with “anti-gray” formula, easy-iron compositions, compositions with special fragrance release, compositions with improved soil removal or preventing re-soiling, antibacterial compositions, UV-protection compositions, color freshening compositions etc.

Since sheet like textile structures, especially those of rayon, viscose rayon, cotton and blends thereof, may tend to crease, because the individual fibers are susceptible to bending, buckling, compressing and pinching transverse to the fiber direction, the compositions produced in accordance with the invention may comprise synthetic crease control agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides, or fatty alcohols, which are usually reacted with ethylene oxide, or else products based on lecithin or on modified phosphoric esters.

In order to combat microorganisms, the compositions produced in accordance with the invention may comprise antimicrobial active substances. In this context, a distinction is made, depending on antimicrobial spectrum and mechanism of action, between bacteriostats and bactericides, fungiostats and fungicides, etc. Examples of important substances in these groups are benzalkonium chlorides, alkylarylsulfonates, halophenols, and phenylmercuric acetate, it also being possible to dispense with these compounds entirely.

Suitable antimicrobial active agents are preferably chosen from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen acetals, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl carbamate, iodine, iodophores, peroxy compounds, halogen compounds and any mixtures thereof.

Consequently, the antimicrobial active substances can be chosen among ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylenelycol, glycerin, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, α-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2′-methylene-bis-(6-bromo-4-chlorophenol), 4,4′-dichloro-2′-hydroxydiphenyl ether (dichlosan), 2,4,4′-trichloro-2′-hydroxydiphenyl ether (trichlosan), chlorhexidine, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)-urea, N,N′-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octamine) dihydrochloride, N,N′-bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraaza-tetradecanediimideamide, glucoprotamines, surface-active antimicrobial quaternary compounds, guanidines, including the bi- and polyguanidines, such as for example 1,6-bis(2-ethylhexylbiguanidohexane) dihydrochloride, 1,6-di-(N₁′,N₁′-phenyldiguanido-N₅,N₅′)hexame tetrahydrochloride, 1,6-di-(N₁, N₁-phenyl-N₁, N₁-methyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-[N₁,N₁′-β-(p-methoxyphenyl)diguanido-N₅,N₅′]hexane dihydrochloride, 1,6-di-(N₁,N₁′-α-methyl-β-phenyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-(N₁,N₁′-p-nitrophenyldiguanido-N₅,N₅′)hexane dihydrochloride, ω:ω-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)di-n-propyl ether dihydrochloride, ω:ω-di-(N₁,N_(1′)-p-chlorophenyldiguanido-N₅,N₅′)di-n-propyl ether tetrahydrochloride, 1,6-di-(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexane tetrahydrochloride, 1,6-di-(N₁,N₁′-p-methylphenyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-(N₁,N₁′-2,4,5-trichlorophenyldiguanido-N₅,N₅′)hexane tetrahydrochloride, 1,6-di-[N₁,N₁′-α-(p-chlorophenyl)ethyldiguanido-N₅,N₅′]hexane dihydrochloride, ω:ω-di-(N₁,N₁′-p-chlorophenyldiguanido-N₅,N_(5′))m-xylene dihydrochloride, 1,12-di-(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)dodecane dihydrochloride, 1,10-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)decane tetrahydrochloride, 1,12-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)dodecane tetrahydrochloride, 1,6-di-(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride, 1,6-di-(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)hexane tetrahydrochloride, ethylene-bis-(1-tolylphenylbiguanide), ethylene-bis-(p-tolylphenylbiguanide), ethylene-bis-(3,5-dimethylphenylbiguanide), ethylene-bis-(p-tert-amylphenylbiguanide), ethylene-bis-(nonylphenylbiguanide), ethylene-bis-(phenylbiguanide), ethylene-bis-(N-butylphenylbiguanide), ethylene-bis-(2,5-diethoxyphenylbiguanide), ethylene-bis-(2,4-dimethylphenylbiguanide), ethylene-bis-(o-diphenylbiguanide), ethylene-bis-(mixed amylnaphthylbiguanide), N-butylethylene-bis-(phenylbiguanide), trimethylene bis(o-tolylbiguanide), N-butyltrimethylene-bis-(phenylbiguanide) and the corresponding salts like acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-coco alkyl sarcinosates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates as well as any mixtures thereof. Furthermore, halogenated xylene- and cresol derivatives are suitable, such as p-chloro-meta-cresol, p-chloro-meta-xylene, as well as natural antimicrobial active agents of plant origin (e.g. from spices or aromatics), animal as well as microbial origin. Preferred antimicrobial agents are antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of vegetable origin and/or a natural antimicrobial agent of animal origin and, most preferably, at least one natural antimicrobial agent of vegetable origin from the group comprising caffeine, theobromine and theophylline and essential oils, such as eugenol, thymol and geraniol, and/or at least one natural antimicrobial agent of animal origin from the group comprising enzymes, such as protein from milk, lysozyme and lactoperoxidase and/or at least one antimicrobial surface-active quaternary compound containing an ammonium, sulfonium, phosphonium, ibdonium or arsonium group, peroxy compounds and chlorine compounds. Substances of microbial origin, so-called bacteriozines, may also be used.

The quaternary ammonium compounds (QUATS) suitable as antimicrobial agents have the general formula (R¹)(R²)(R³)(R⁴)N⁺X⁻, in which R¹ to R⁴ may be the same or different and represent C₁₋₂₂ alkyl groups, C₇₋₂₈ aralkyl groups or heterocyclic groups, two or—in the case of an aromatic compound, such as pyridine—even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X⁻ represents halide ions, sulfate ions, hydroxide ions or similar anions. In the interests of optimal antimicrobial activity, at least one of the substituents preferably has a chain length of 8 to 18 and, more preferably, 12 to 16 carbon atoms.

QUATS can be obtained by reacting tertiary amines with alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide and also ethylene oxide. The alkylation of tertiary amines having one long alkyl chain and two methyl groups is particularly easy. The quaternization of tertiary amines containing two long chains and one methyl group can also be carried out under mild conditions using methyl chloride. Amines containing three long alkyl chains or hydroxy-substituted alkyl chains lack reactivity and are preferably quaternized with dimethyl sulfate.

Suitable QUATS are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzyl ammonium chloride, CAS No. 8001-54-5), benzalkon B (m,p-dichlorobenzyl dimethyl-C₁₂-alkyl ammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecyl-bis-(2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethyl ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N,N-di-methyl-N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)-phenoxy]-ethoxy]-ethyl]-benzyl ammonium chloride, CAS No. 121-54-0), dialkyl dimethyl ammonium chlorides, such as di-n-decyldimethyl ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl ammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 1576448-1) and mixtures thereof. Particularly preferred QUATS are the benzalkonium chlorides containing C₈₋₁₈ alkyl groups, more particularly C₁₂₋₁₄ alkyl benzyl dimethyl ammonium chloride.

Benzalkonium halides and/or substituted benzalkonium halides are commercially obtainable, for example, as Barquat® from Lonza, Marquato® from Mason, Variquat® from Witco/Sherex and Hyamine® from Lonza and as Bardac® from Lonza. Other commercially obtainable antimicrobial agents are N-(3-chloroallyl)-hexaminium chloride, such as Dowicide® and Dowicil® from Dow, benzethonium chloride, such as Hyamine® 1622 from Rohm & Haas, methyl benzethonium chloride, such as Hyamine® 10X from Rohm & Haas, cetyl pyridinium chloride, such as cepacolchloride from Merrell Labs.

The antimicrobial agents are used in quantities of normally 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.8% by weight, more preferably 0.005% by weight to 0.3% by weight and most preferably 0.01 to 0.2% by weight.

In order to prevent unwanted changes to the compositions and/or the treated textiles resulting from oxygen exposure and other oxidative processes, the compositions may comprise antioxidants. This class of compound includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, and phosphonates.

Increased wear comfort may result from the additional use of antistats, which are additionally added to the compositions produced in accordance with the invention. Antistats increase the surface conductivity and thus enable better dissipation of charges that are formed. External antistats are generally substances having at least one hydrophilic molecule ligand, and provide a more or less hygroscopic film on the surfaces. These antistats, which are usually interface-active, may be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric esters), and sulfur-containing (alkylsulfonates, alkyl sulfates) antistats. The lauryl- (or stearyl-) dimethylbenzyl ammonium chlorides are suitable as antistats for textiles and as additives to laundry detergents, in which additionally, a finishing effect is obtained.

In order to improve the water absorption capacity, the rewettability of the treated textiles, and to facilitate ironing of the treated textiles, silicone derivatives, for example, may be used in the compositions produced in accordance with the invention. These derivatives, by virtue of their foam inhibiting properties, additionally improve the rinse-out behavior of the compositions. Examples of preferred silicone derivatives are polydialkylsiloxanes or alkylarylsiloxanes where the alkyl groups have one to five carbon atoms and are totally or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may, if desired have been derivatized, and in that case are amino-functional or quaternized, or have Si—OH, Si—H and/or Si—Cl bonds. The viscosities of the preferred silicones at 25° C. are in the range between 100 and 100 000 centistokes, it being possible to use the silicones in amounts of between 0.2 and 5% by weight, based on the overall composition.

Finally, the compositions produced in accordance with the invention may also comprise UV absorbers, which attach to the treated textiles and improve the light stability of the fibers. Compounds, which exhibit these desired properties, are, for example, the compounds, which are active via radiationless deactivation, and derivatives of benzophenone having substituents in position(s) 2 and/or 4. Also suitable are substituted benzotriazoles, acrylates, which are phenyl-substituted in position 3 (cinnamic acid derivatives), with or without cyano groups in position 2, salicylates, organic Ni complexes, as well as natural substances such as umbelliferone and the endogenous urocanic acid.

A further embodiment of the present invention is a process for the manufacture of water-soluble portion packaging with at least one core therein and a matrix of a free-flowing material, at least partially surrounding the core(s), characterized by the steps

-   -   a) Manufacture of a water-soluble material based portion         packaging open on one side.     -   b) Filling up the portion packaging with one or more cores as         well as fixing the core or cores;     -   c) Filling the portion packaging with the free-flowing matrix;     -   d) Sealing the portion packaging.

The portion packaging, open on one side, can be manufactured by established thermoforming processes of polymers, wherein deep drawing, the process known as the rotary die process, blow molding (blown extrusion) and injection molding are of particular importance. The following embodiments are based on the particularly preferred manufacture by the injection molding process, but are also valid mutatis mutandis for the other thermoforming process known from the state of the art.

The portion packaging that is open on one side can be manufactured according to the invention by e.g. blow molding, injection molding, deep drawing or calendering. Suitable blow molding processes include extrusion blowing, co-extrusion blowing, injection-stretch blowing and dip molding; Injection molding is a known processing method at high pressures and temperatures, involving the steps of closing the injection mold attached to the end of the extruder, injecting the polymer at elevated temperature and high pressure, cooling the injection-molded part, opening the mold and removing the molded part. Other optional steps, such as the application of mold release agents, ejection from the mold etc., are known to the expert and can be carried out using known technology.

Preferred processes according to the invention are characterized in that the portion packaging that is open on one side is manufactured by injection molding or thermoforming processes, preferably deep drawing.

The core—as explained above in detail—can be manufactured, for example by tabletting or casting processes, but can also be a gelatin capsule or similar. Preferred processes according to the invention are characterized in that the core is manufactured by tabletting.

With respect to fixing the core, reference can be made to the above embodiments. Processes according to the invention are preferred in which the core is fixed to the water-soluble envelope by positioning the core in a shaped cavity of the envelope. Processes are also preferred in which the core is fixed to the water-soluble envelope by positioning the core in one of the envelopes and subsequently shrinking back the envelope material, as well as processes in which the core is fixed to the water-soluble envelope by an adhesive bonding.

The closure in step d) is effected by sealing with a thin, water-soluble film, by means of a “plug” to close the opening, or by any other established method. Preferred processes according to the invention are characterized in that the closure of the filled packaging is made by sealing on a film, whose thickness preferably ranges from 10 to 100 μm, especially preferred from 20 to 75 μm and particularly from 30 to 50 μm.

As used herein, and in particular as used herein to define the elements of the claims that follow, the articles “a” and “an” are synonymous and used interchangeably with “at least one” or “one or more,” disclosing or encompassing both the singular and the plural, unless specifically defined otherwise. The conjunction “or” is used herein in its inclusive disjunctive sense, such that phrases formed by terms conjoined by “or” disclose or encompass each term alone as well as any combination of terms so conjoined, unless specifically defined otherwise. All numerical quantities are understood to be modified by the word “about,” unless specifically modified otherwise or unless an exact amount is needed to define the invention over the prior art. 

1. A portioned package of an active ingredient, comprising a sealed water-soluble envelope containing at least one core and a matrix of a free-flowing material at least partially surrounding the core, the core and matrix together comprising one or more active ingredients, wherein the core is fixed to the water-soluble envelope.
 2. The portioned package of claim 1, wherein the water-soluble envelope comprises one or more materials selected from the group consisting of (optionally acetalized) polyvinyl alcohol (PVAL) and/or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose, and any derivatives and/or mixtures thereof.
 3. The portioned package of claim 2, wherein the water-soluble envelope comprises methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose, or any combination thereof.
 4. The portioned package of claim 1, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a degee of hydrolysis of 70 to 100 molar %.
 5. The portioned package of claim 4, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a degee of hydrolysis of 80 to 90 molar %.
 6. The portioned package of claim 5, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a degee of hydrolysis of 81 to 89 molar %.
 7. The portioned package of claim 6, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a degee of hydrolysis of 82 to 88 molar %.
 8. The portioned package of claim 1, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having a molecular weight of 3500 to 100,000 gmol⁻¹.
 9. The portioned package of claim 8, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having a molecular weight of 10,000 to 90,000 gmol⁻¹.
 10. The portioned package of claim 9, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having a molecular weight of 12,000 to 80,000 gmol⁻¹.
 11. The portioned package of claim 10, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having a molecular weight of 13,000 to 70,000 gmol⁻¹.
 12. The portioned package of claim 1, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having an average polymerization degree of 80 and
 700. 13. The portioned package of claim 12, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having an average polymerization degree of 150 and
 400. 14. The portioned package of claim 13, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or PVAL copolymer having an average polymerization degree of 180 and
 300. 15. The portioned package of claim 1, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a molecular weight ratio MG(50%) to MG(90%) of 0.3 and
 1. 16. The portioned package of claim 15, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a molecular weight ratio MG(50%) to MG(90%) of 0.4 and 0.8.
 17. The portioned package of claim 16, wherein the water-soluble envelope comprises a polyvinyl alcohol and/or a PVAL copolymer having a molecular weight ratio MG(50%) to MG(90%) of 0.45 and 0.6.
 18. The portioned package of claim 1, wherein the water-soluble envelope comprises a hydroxypropyl methylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of 1.0 to 2.0.
 19. The portioned package of claim 18, wherein the HPMC has a degree of substitution of 1.4 to 1.9, and a degree of molar substitution of 0.15 to 0.25.
 20. The portioned package of claim 1, wherein the water-soluble envelope comprises a film material having a thickness from 10 to 1000 μm.
 21. The portioned package of claim 20, wherein the water-soluble envelope comprises a film material having a thickness of 20 to 750 μm.
 22. The portioned package of claim 21, wherein the water-soluble envelope comprises a film material having a thickness of 30 to 500 μm.
 23. The portioned package of claim 1, wherein the core comprises a tablet.
 24. The portioned package of claim 1, wherein the core comprises a solidified melt.
 25. The portioned package of claim 1, wherein the core is sterically delimited by means of an internal partition wall or a weir.
 26. The portioned package of claim 1, wherein the core is fixed to the water-soluble envelope by positioning the core in a shaped cavity of the envelope.
 27. The portioned package of claim 1, wherein the core is fixed to the water-soluble envelope by shrinking the envelope material.
 28. The portioned package of claim 1, wherein the core is fixed to the water-soluble envelope by an adhesive bonding.
 29. The portioned package of claim 1, wherein the free-flowing material comprises a liquid having a viscosity of 500 to 50,000 mPas.
 30. The portioned package of claim 1, wherein the free-flowing material comprises a liquid having a viscosity of 1000 to 10,000 mPas.
 31. The portioned package of claim 1, wherein the free-flowing material comprises a liquid having a viscosity of 1200 to 5000 mPas.
 32. The portioned package of claim 1, wherein the free-flowing material comprises a liquid having a viscosity of 1300 to 3000 mPas.
 33. The portioned package of claim 1, wherein the free-flowing material comprises a solidified melt.
 34. The portioned package of claim 1, wherein the free-flowing material comprises a bulk of particles having a mean particle size of below 1200 μm.
 35. The portioned package of claim 34, wherein the free-flowing material comprises a bulk of particles having a mean particle size of below 300 μm.
 36. The portioned package of claim 35, wherein the free-flowing material comprises a bulk of particles having a mean particle size of below 250 μm.
 37. The portioned package of claim 36, wherein the free-flowing material comprises particles having a mean particle size of below 200 μm.
 38. A process for the manufacture of water-soluble portion packagings, comprising the steps of: a) forming a water-soluble envelope comprising a water-soluble material; b) filling the envelope with one or more cores and fixing one or more of cores to the envelope; c) filling the envelope with a matrix of free-flowing material; and d) sealing the envelope.
 39. The process of claim 38, wherein the envelpe is formed by injection molding, thermoforming, or deep-drawing.
 40. The process of claim 38, wherein the core is made by tabletting.
 41. The process of claim 38, wherein the core is fixed to the water-soluble envelope by positioning the core in a shaped cavity of the envelope.
 42. The process of claim 41, wherein after the core is fixed to the water-soluble envelope by positioning the envelope material is shrunk around the core.
 43. The process of claim 38, wherein the core is fixed to the water-soluble envelope by an adhesive bonding. 